Application of porous structured organic films for gas storage

ABSTRACT

A porous structured organic film for storing gaseous a gaseous entity and method for storing gaseous entities in a porous structured organic film, the porous structured organic film including a plurality of segments and a plurality of linkers arranged as a covalent organic framework, wherein at a macroscopic level the covalent organic framework is a film and contains a plurality of sites accessible to one or more gaseous entity.

CROSS-REFERENCE TO RELATED APPLICATIONS

This nonprovisional application is related to U.S. patent applicationSer. Nos. 12/716,524; 12/716,449; 12/716,706; 12/716,324; 12/716,686;12/716,571; 12/815,688; 12/845,053; 12/845,235; 12/854,962; 12/854,957;and 12/845,052 entitled “Structured Organic Films,” “Structured OrganicFilms Having an Added Functionality,” “Mixed Solvent Process forPreparing Structured Organic Films,” “Composite Structured OrganicFilms,” “Process For Preparing Structured Organic Films (SOFs) Via aPre-SOF,” “Electronic Devices Comprising Structured Organic Films,”“Periodic Structured Organic Films,” “Capped Structured Organic FilmCompositions,” “Imaging Members Comprising Capped Structured OrganicFilm Compositions,” “Imaging Members for Ink-Based Digital PrintingComprising Structured Organic Films,” “Imaging Devices ComprisingStructured Organic Films,” and “Imaging Members Comprising StructuredOrganic Films,” respectively; and U.S. Provisional Application No.61/157,411, entitled “Structured Organic Films” filed Mar. 4, 2009, thedisclosures of which are totally incorporated herein by reference intheir entireties.

BACKGROUND OF THE INVENTION

Porous materials have a comparatively large specific surface area, andthus can adsorb large quantities of gas or small organic molecules. Suchporous materials may be useful for applications including gas storage,gas separation, ion transport membranes and, in general, applicationswhere trapping or transporting a chemical entity through a material isrequired. Additionally, porous materials may be useful for otherapplications, such as dielectrics, novel composites (e.g. P/R, fusing,drug release), supercapacitors, or catalysis. Most permanently porousmaterials are usually inorganic compounds, obtained as refractorypowders that need to be imbedded into other materials to create films sothey can be appropriated for device integration (e.g. electronics, fuelcells, batteries, gas separation membranes, etc.).

Typical porous materials comprise microporous materials having pore sizeless than 2 nm, mesoporous materials having pore size between 2 nm and50 nm, and macroporous materials having pore size bigger than 50 nm. In1995, Omar Yaghi synthesized the MOF (metal-organic-framework)(referring to Nature, 1995, (378), 703), a metal-organic coordinationpolymer that is really close to practical application. As a newfunctional molecular material, the MOF not only has a crystal structuresimilar to the zeolite molecular sieve, but also its structure iscapable of being designed. The MOF can obtain nano-size pore channelsand cavities by directionally designing the topological structure andexpanding the organic functional groups. However, the MOF has acomparative poor chemical stability. In 2005, Omar Yaghi disclosed theCOF (covalent organic framework) (referring to Science, 2005, (310),1166), an organic porous framework material, which is composed of lightelements (C, H, O, B) being connected via covalent bonds. However, thechemical stability problem is not really solved.

COFs, differ from polymers/cross-linked polymers in that COFs areintended to be highly patterned. In COF chemistry molecular componentsare called molecular building blocks rather than monomers. During COFsynthesis molecular building blocks react to form two- orthree-dimensional networks. Consequently, molecular building blocks arepatterned throughout COF materials and molecular building blocks arelinked to each other through strong covalent bonds.

COFs developed thus far are typically powders with high porosity and arematerials with exceptionally low density. COFs can store near-recordamounts of argon and nitrogen. While these conventional COFs are useful,there is a need, addressed by embodiments of the present invention, fornew materials that offer advantages over conventional COFs in terms ofenhanced characteristics.

The properties and characteristics of conventional COFs are described inthe following documents:

Yaghi et al., U.S. Pat. NO. 7,582,798;

Yaghi et al., U.S. Pat. No. 7,196,210;

Shun Wan et al., “A Belt-Shaped, Blue Luminescent, and SemiconductingCovalent Organic Framework,” Angew. Chem. Int. Ed., Vol. 47, pp.8826-8830 (published on web Jan. 10, 2008);

Nikolas A. A. Zwaneveld et al., “Organized Formation of 2D ExtendedCovalent Organic Frameworks at Surfaces,” J. Am. Chem. Soc., Vol. 130,pp. 6678-6679 (published on web Apr. 30, 2008);

Adrien P. Cote et al., “Porous, Crystalline, Covalent OrganicFrameworks,” Science, Vol. 310, pp. 1166-1170 (Nov. 18, 2005);

Hani El-Kaderi et al., “Designed Synthesis of 3D Covalent OrganicFrameworks,” Science, Vol. 316, pp. 268-272 (Apr. 13, 2007);

Adrien P. Cote et al., “Reticular Synthesis of Microporous andMesoporous Covalent Organic Frameworks” J. Am. Chem. Soc., Vol. 129,12914-12915 (published on web Oct. 6, 2007);

Omar M. Yaghi et al., “Reticular synthesis and the design of newmaterials,” Nature, Vol. 423, pp. 705-714 (Jun. 12, 2003);

Nathan W. Ockwig et al., “Reticular Chemistry: Occurrence and Taxonomyof Nets and Grammar for the Design of Frameworks,” Acc. Chem. Res., Vol.38, No. 3, pp. 176-182 (published on web Jan. 19, 2005);

Pierre Kuhn et al., ‘Porous, Covalent Triazine-Based Frameworks Preparedby Ionothermal Synthesis,” Angew. Chem. Int. Ed., Vol. 47, pp.3450-3453. (Published on web Mar. 10, 2008);

Jia-Xing Jiang et al., “Conjugated Microporous Poly(aryleneethylnylene)Networks,” Angew. Chem. Int. Ed.,

Vol. 46, (2008) pp, 1-5 (Published on web Sep. 26, 2008);

Hunt, J. R. et al. “Reticular Synthesis of Covalent-Organic BorosilicateFrameworks” J. Am. Chem. Soc., Vol. 130, (2008), 11872-11873. (publishedon web Aug. 16, 2008); and

Colson et al. “Oriented 2D Covalent Organic Framework Thin Films onSingle-Layer” Science, 332, 228-231 (2011).

Gas storage materials that are being developed are currently powdersthat need to be compacted or shaped and subsequently inserted intocylindrical containers for use. Considerable benefit in optimizing thestorage system geometry and footprint can be accessed if the gas storagematerial were in a form other than a powder, such as a film. Thus,improvements are still needed over the conventional porous materials.

SUMMARY OF THE DISCLOSURE

There is provided, in embodiments, methods for storing a gaseous entity,the methods comprising: contacting the gaseous entity with a sorbentmaterial, the sorbent material comprising a porous structured organicfilm (SOF) comprising a plurality of segments including at least a firstsegment type and a plurality of linkers including at least a firstlinker type arranged as a covalent organic framework (COF), and aplurality of pores, wherein the first segment type and/or the firstlinker type comprises at least one atom that is not carbon, and theplurality of pores comprises a plurality of accessible sites for uptakeand storage of the gaseous entity; and storing the gaseous entity for apredetermined duration.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present disclosure will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent illustrative embodiments:

FIG. 1A-O are illustrations of exemplary building blocks whosesymmetrical elements are outlined.

FIG. 2 is an illustration of a carbon dioxide gas adsorption isothermfor the SOF of Example 1.

FIG. 3 an illustration of the pore size distribution for the SOF ofExample 1.

DETAILED DESCRIPTION

In this specification and the claims that follow, singular forms such as“a,” “an,” and “the” include plural forms unless the content clearlydictates otherwise.

The term “SOF” or “SOF composition” generally refers to a covalentorganic framework (COF) that is a film at a macroscopic level. However,as used in the present disclosure the term “SOF” does not encompassgraphite, graphene, and/or diamond. The phrase “macroscopic level”refers, for example, to the naked eye view of the present SOFs. AlthoughCOFs are a network at the “microscopic level” or “molecular level”(requiring use of powerful magnifying equipment or as assessed usingscattering methods), the present SOF is fundamentally different at the“macroscopic level” because the film is for instance orders of magnitudelarger in coverage than a microscopic level COF network. SOFs describedherein that may be used in the embodiments described herein are solventresistant and have macroscopic morphologies much different than typicalCOFs previously synthesized.

As used herein, “sorption” is a general term that refers, for example,to a process resulting in the association of atoms or molecules with atarget material. Sorption includes both adsorption and absorption.Absorption refers to a process in which atoms or molecules move into thebulk of a porous material, such as the absorption of water by a sponge.Adsorption refers to a process in which atoms or molecules move from abulk phase (that is, solid, liquid, or gas) onto a solid or liquidsurface. The term adsorption may be used in the context of solidsurfaces in contact with liquids and gases. Molecules that have beenadsorbed onto solid surfaces are referred to generically as adsorbates,and the surface to which they are adsorbed as the substrate oradsorbent. Adsorption is usually described through isotherms, that is,functions that connect the amount of adsorbate on the adsorbent, withits pressure (if gas) or concentration (if liquid). In general,desorption refers to the reverse of adsorption, and is a process inwhich molecules adsorbed on a surface are transferred back into a bulkphase.

The porous SOF(s) of the present disclosure can be used for a variety ofapplications where storing (and optionally releasing) a gaseous entity,trapping (and optionally releasing) a gaseous entity, selecting orpurifying (and optionally releasing) a specific gaseous entity, and/ortransporting a gaseous entity may be desired or required. The SOFs ofthe present disclosure offer considerable opportunity to accessbeneficial designs for gas storage systems, especially for mobileapplications.

The term “gaseous entity” refers, for example, any molecules and/orbiological substances, including ions and radicals thereof, that may beintroduced into the gas phase, either with or without the aid ofincreased temperature and/or reduced pressure, such as gaseous chemicalentities.

The term “gaseous chemical entity” refers, for example, any molecules,including ions and radicals thereof, that may be introduced into the gasphase, either with or without the aid of increased temperature and/orreduced pressure.

The term “uptake” refers, for example, to a process resulting in theassociation of a gaseous entity, such as gaseous chemical entity and/ortarget gaseous entity, with a sorbent material, such as a sorbentmaterial tailored to selectively associate with the target gaseousentity,

The porous SOF(s) of the present disclosure may be used to adsorb orabsorb gaseous entities (or gaseous chemical species). The porous SOF(s)of the present disclosure may be exposed to conditions under which thegaseous entities are desorbed from the porous SOF(s).

In embodiments, the porous SOF(s) of the present disclosure may beincorporated into devices for the uptake of a gaseous entity. Inembodiments, the porous SOF(s) of the present disclosure may beincorporated into devices for the uptake of one or more types of gaseousentities.

In embodiments, the present disclosure provides a device that mayinclude a sorbent material comprising at least one porous SOF of thepresent disclosure. In embodiments, the uptake of one or more gaseousentities into the sorbent material, such as a sorbent materialcomprising at least one porous SOF, may be reversible or non-reversible.

In embodiments, the sorbent material, such as a sorbent materialcomprising at least one porous SOF, in the device may be included indiscrete layers. In embodiments, the sorbent material, such as a sorbentmaterial comprising at least one porous SOF, in the device may beembedded into or fixed to a gas-permeable three-dimensional support,which may or may not be a SOF. In embodiments, the sorbent material,such as a sorbent material comprising at least one porous SOF, may havepores for the reversible uptake or storage gases. In embodiments, thesorbent material, such as a sorbent material comprising at least oneporous SOF, of the present disclosure may reversibly adsorb or absorbgases.

In embodiments, a device provided herein comprises a storage unit forthe storage of one or more gaseous entities, such as, small moleculesincluding, for example, ammonia, carbon dioxide, carbon monoxide,hydrogen, amines, methane, natural gas, oxygen, argon, nitrogen, and/orargon, and/or other larger molecules such as those commonly known asvolatile organic compounds (VOCs), alkanes, petroleum, halogenatedhydrocarbons. Certain embodiments may also comprise a storage system formixtures of one or more gaseous entities. In embodiments, the one ormore gaseous entities may be stored in the SOFs of the presentdisclosure for a predetermined time, such as predetermined number ofseconds, minutes, hours, days or years.

Adsorptive gas storage relies on the physical phenomena wherein anysurface will, in an energetically favorable means, adsorb gas molecules.If a material that is created that has internal surface area (i.e.porous) it has a much greater capacity to hold onto gas molecules than adense material with just external surface area. In a gas storage systemit is desirable to store large amounts of gasses at lowered pressuresfor safety reasons. Porous adsorbents are pursued for hydrogen andmethane gas storage systems for vehicular and mobile applicationsbecause their internal surface areas have the ability, via theaforementioned adsorptive process, to concentrate gases at pressureslower than a gas' natural compressibility.

The term “natural compressibility” of a gas refers, for example, to thenominal behavior of a gas when put under increased pressure. Undercompression the concentration of gaseous entities increases: within agiven volume there it is possible to store more gaseous entities at ahigher pressure than at a lowered pressure. It is well known in the artthat a porous material has the ability to further concentrate gaseousentities at a given pressure by offering adsorptive sites within itsinternal surfaces. Thus within pore volume of a porous material it ispossible to concentrate a gaseous entity beyond its naturalcompressibility.

In embodiments, the gaseous chemical entity is present in the SOF at aconcentration from about 1.05 times greater than the naturalcompressibility of the gaseous chemical entity to about theconcentration of the gaseous chemical entity upon its liquification,such as from about 1.1 times greater than the natural compressibility ofthe gaseous chemical entity to about the concentration of the gaseouschemical entity upon its liquification, or from about 1.5 times greaterthan the natural compressibility of the gaseous chemical entity to aboutthe concentration of the gaseous chemical entity upon its liquification.

Unlike conventional adsorptive powders, which generally require acylindrical tank, the porous SOFs of the present disclosure are notlimited in their applicability for mobile applications. For example, theporous SOFs of the present disclosure may be present in alternategeometries for gas storage systems such that the porous SOFs of thepresent disclosure can be seamlessly integrated into the device/vehiclebecause SOFs can be conformably introduced to the vehicular system (e.g.integrated into structural components), or alternatively SOFs sheets canbe adapted to function as storage material included in current storagegeometries, such as cylindrical tanks or the like.

In embodiments, methods for the uptake of one or more gaseous entitiesinto sorbent material(s) comprising at least one porous SOF areprovided. In embodiments, methods for the uptake of one or more gaseousentities into sorbent material(s) comprising at least one porous SOF areprovided such that the one or more gaseous entities may be stored in thesorbent material(s) comprising at least one porous SOF. In embodiments,the methods of the present disclosure include contacting a sorbentmaterial that includes at least one porous SOF of the present disclosurewith one or more gaseous entities. In embodiments, the uptake of the oneor more gaseous entities may include storage of the one or more gaseousentities. In embodiments, the one or more gaseous entities are storedunder conditions suitable for use as an energy source.

In embodiments, in the methods of separation of the present disclosure,the one or more gaseous entity is contacted with the sorbent materialcomprising a SOF of the present disclosure.

In embodiments, the one or more gaseous entities utilized in the methodsof the present disclosure may comprise a mixture of one or more targetgaseous entities and one or more non-target gaseous entities. Inembodiments, the porous SOFs of the present disclosure may comprise aplurality of pores having a plurality of accessible sites for selectiveuptake of the target gaseous entity. In further embodiments, the methodsof the present disclosure may include contacting a gaseous entity with asorbent material by diffusing the one or more target gaseous entitiesinto the plurality of accessible sites for the selective uptake of theone or more target gaseous entities. In embodiments, the one or moretarget gaseous entities may be contaminant(s).

In specific embodiments, the non-target gaseous entities may comprise acomposition of molecules where purification is desired. For example, inthe methods of the present disclosure the non-target gaseous entitiesmay comprise water, and the step of contacting the gaseous entity with asorbent material may include contacting water vapor feed stream with thesorbent material and diffusing the water vapor through the sorbentmaterial in order to purify the water vapor by selectively uptake theone or more target gaseous entities, which may be contaminants.

In embodiments, methods are provided for the uptake of gaseous entitiesthat include contacting a device comprising a porous SOF of the presentdisclosure with the gaseous entities.

In embodiments, the segments of the SOFs of the present disclosure maybe functionalized in order to create sites with a desired property (suchas, for example, a specific electric or steric property). This abilityof SOFs to be functionalized is useful in many storage, separation,and/or catalytic applications because the pores may be lined with a highconcentration of ordered sites whose properties, such as hydrophobic,hydrophilic, polar, non-polar, electronic, steric properties, as well asother properties that may be varied in SOFs (as described below), can betailored by functionalization of the segments and linkers of the SOF.

The porous SOFs of the present disclosure have advantages over both ofinorganic zeolites and of MOFs (such as higher stability andparticularly hydrolytic stability), and thus may be applied to highlyefficient catalysis, separations and storage applications. Inembodiments, the porous SOFs of the present disclosure may possess ananoporous structure useful for filtration, gas storage and the like. Inembodiments pore sizes may range from about 4 Angstroms to about 40Angstroms, such as from about 6 Angstroms to about 30 Angstroms, or fromabout 7 Angstroms to 20 Angstroms. In embodiments, the porous SOFs haveexceptional chemical stability, exceeding MOFs and COFs, in refluxingpolar solvents, non-polar solvents, acidic solvents, basic solvents,organic solvents, and water.

In embodiments, the building blocks that are reacted to form the porousSOF may provide organically lined cages and channels of a predeterminedsize and shape. In embodiments, specific building blocks may be selectedand/or further functionalized such that function groups line the cagesand channels, and/or the pores. In embodiments, specific building blocksmay be selected and/or further functionalized such that a desired SOFstructure with a predetermined pore size is obtained.

For example, the porous SOFs of the disclosure may comprise one or moreof the following characteristics: a surface area of the plurality ofpores is greater than about 75 m²/g; a surface area of the plurality ofpores is about 75 to about 3500 m²/g; a surface area of the plurality ofpores is about 150 to about 2000 m²/g; an average pore volume of theplurality of pores comprising the porous SOF is in the range from about0.05 to about 1.7 cm³/g, such as about 0.1 to about 1.6 cm³/g; theframework of the porous SOF has a density in a range of from about 0.3to about 1.5 g/cm³.

In embodiments, the porous SOFs of the disclosure comprise a thermalstability range of at least up to 200° C., or a thermal stability rangeof at least up to 300° C., such as a thermal stability range of greaterthan about 250 to about 700° C., such as a thermal stability range ofgreater than from about 300 to about 450° C. In embodiments, the porousSOFs of the disclosure comprise a Langmuir surface area of about 75 m²/gto about 3500 m²/g.

In embodiments, a gas storage and/or gaseous separation materialcomprising a porous SOF is provided. In embodiments, a porous SOF of thepresent disclosure may include one or more sites for storing orseparating gas molecules. For example, the building blocks may befunctionalized such that function groups of the SOFs form the one ormore sites for storing or separating gas molecules. In embodiments, thegases that may be stored in the gas storage material of the presentdisclosure may include polar gases, nonpolar gases, and/or gas moleculescomprising available electron density for attachment to the one or moresites on the surface area of a pore of the porous SOF. Such electrondensity may include molecules having multiple bonds between two atomscontained therein or molecules having a lone pair of electrons. Suitableexamples of such gases include, but are not limited to, the gasescomprising a component selected from the group consisting of ammonia,argon, methane, natural gas, water, nitrogen, oxygen, hydrogen sulfide,thiophene, sulfur dioxide, carbon dioxide, carbon monoxide, hydrogen,and combinations thereof.

In embodiments, porous SOFs may be used to store gaseous entities(gases, hydrocarbons, molecules, atoms, and the like). The storagecapacity of the porous SOFs may be described in terms of the percentageof the available pore volume that is occupied by gaseous entities. Forexample, when the entire available pore structure of a porous SOF isoccupied then the SOF may be described as being at 100% filling orstorage capacity. The pore volume of an SOF may be defined, for example,as the ratio of the volume of pores/mass of SOF (cm³/g), and thisquantity may be determined from gas adsorption measurements. The volumeof the SOF pore structure occupied by a gaseous entity can be determinedby measuring the mass change of a porous SOF upon its exposure to agaseous entity and calculating the corresponding volume of gaseousentity by using known or calculated values of molecular volume. Anydegree of filling capacity may be selected for the porous SOFs of thepresent disclosure. In embodiments, a loaded porous SOF-based gaseousentity storage system may have a filling capacity in the range of fromabout 40% to about 100%, or about 60% or about 100%, or about 80 toabout 95%.

In embodiments, the gas storage material comprising a porous SOF may bea material that may also be used to separate the desired gas from agaseous mixture, such as a gas storage material that may be used tocollect the gas (from a gaseous mixture) that is to be stored. Forexample, in embodiments, the gas storage material comprising a porousSOF is a hydrogen storage material that is used to store hydrogen (H₂),and optionally the gas storage material comprising a porous SOF is a H₂storage material that may be used to separate (from a gaseous mixture)the H₂ gas to be stored. In embodiments, the gas storage material may bea carbon dioxide (CO₂) storage material, such as a CO₂ storage materialthat may be used to separate (from a gaseous mixture) the CO₂ to bestored.

In contrast to conventional gas separation processes, which use powdersthat need to be imbedded into other materials or compacted into shapedbodies, the porous SOFs of the present disclosure may be directly formedin the shape of a film so they can be employed in processes, such aspressure swing adsorption, without further processing, if desired.

Pressure swing adsorption (PSA) processes rely on the fact that underpressure, gases tend to be attracted to solid surfaces, or “adsorbed”.PSA procedures, processes and apparatus are disclosed in U.S. Pat. Nos.3,430,418; 4,917,711; 6,340,382; 6,464,756; and 5,300,271, and U.S.Patent Application Publication Nos. 2003/0126989, 2003/0172808,2005/0257685, 2006/0236862, and 2011/0011128, the disclosures of whichare incorporated by reference in their entireties. The higher thepressure, the more gas is adsorbed; when the pressure is reduced, thegas is released, or desorbed. PSA processes can be used to separategases in a mixture because different gases tend to be attracted todifferent solid surfaces more or less strongly. If a gas mixture such asair, for example, is passed under pressure through a vessel containingan adsorbent bed that attracts nitrogen more strongly than it doesoxygen, part or all of the nitrogen will stay in the bed, and the gascoming out of the vessel will be enriched in oxygen.

Pressure swing adsorption processes selectively ‘filter’ gas moleculesby using a porous material's (adsorbant) inherent affinity towardgasses. The methods, materials, compositions, devices, and systems ofthe present disclosure allow for the achievement of a substantialimprovement in pressure swing adsorption process by employing an sorbentbed comprising a porous SOF that interacts with gas molecules, where thesorbent bed comprising a porous SOF is in the form of a permanentlyporous membrane or film rather than a powder.

In embodiments, when a bed comprising a porous SOF of the presentdisclosure reaches the end of its capacity to adsorb a gas, such asnitrogen, it can be regenerated by reducing the pressure, therebyreleasing the adsorbed gas, such as nitrogen. It is then ready foranother cycle of producing a product enriched with the target gas, suchas oxygen enriched air. This is exactly the process used in portableoxygen concentrators used by emphysema patients and others who requireoxygen enriched air to breathe. PSA is currently limited by using powderadsorbents. For example, in the adsorption bed considerable ‘dead space’exists between particles where no selective adsorption takes place.Thus, to accommodate the optimal mass of the required adsorbent largevolumes are required. Replacing powders with a membrane comprising aporous SOF allows for more efficient compaction of the adsorbent (e.g.rolling/folding/stacking) opening options for new and smallergeometries/footprints for PSA processes, which, in particular, benefitmobile/portable gas separation devices (e.g. oxygen concentrators).

In embodiments, the porous SOFs of the present disclosure may bedirectly formed in a desired shape, such as a film, so they can beemployed in processes, such as a reverse osmosis process, withoutfurther processing, if desired. Reverse osmosis is the process offorcing a solvent from a region of high solute concentration through amembrane to a region of low solute concentration by applying a pressurein excess of the osmotic pressure. This is the reverse of an osmosisprocess, which is the natural movement of solvent from an area of lowsolute concentration, through a membrane, to an area of high soluteconcentration when no external pressure is applied. In embodiments, theporous SOFs of the present disclosure may be semipermeable, meaning theyallow for the passage of solvent but not of solute. In embodiments,porous SOFs of the present disclosure may be a membrane for reverseosmosis, such as a membrane having a dense barrier layer in where mostseparation occurs. The porous SOF membrane may be designed to allow onlywater to pass through this dense layer while preventing the passage ofsolutes, such as salts. The reverse osmosis process generally requiresthat a high pressure be exerted on the high concentration side of themembrane, usually 2-17 bar (30-250 psi) compositions such as fresh andbrackish water, and 40-70 bar (600-1000 psi) for seawater, which hasaround 24 bar (350 psi) natural osmotic pressure which must be overcome.Reverse osmosis procedures, processes and apparatus are disclosed in (J.Kucera, “Reverse Osmosis: Design, Processes, and Applications forEngineers” Wiley-Scrivener, 2010), the disclosure of which areincorporated by reference in their entireties.

In embodiments, a membrane is a selective barrier that is capable ofrestricting or permitting, in any extent, the passage of an entity(gaseous, chemical, biological, or the like) through its structure undera drive force. Driving forces may include, and are not restricted to,pressure gradient, concentration gradient, electromotive force,temperature gradient, or mechanical perturbation.

In embodiments, at least one of the porous SOFs of the presentdisclosure may form a single layer or multilayer membrane. Inembodiments, a membrane comprising a porous SOF, which may be one ormore substantially pinhole-free SOFs or pinhole-free SOFs, may be usedin conjunction with other membranes or with other gas separationtechniques if desired, e.g. with solvent absorption (e.g. Selexol,Rectisol, Sulfinol, Benfield), amine absorption (e.g. DEA, MDEA),physical adsorption, cryogenic techniques, etc. In embodiments, themembranes comprising a porous SOF of the present disclosure are tailored(by, for example selecting specific components, such as building blocks,with known affinities for the target species) for separating a feed gascontaining a target gas into a gas stream rich in the target gas and agas stream depleted in the target gas. For example, membranes comprisinga porous SOF of the present disclosure may be used to separate a feedgas comprising polar and non-polar gases into a gas stream rich in polargases and a gas stream depleted in polar gases.

In embodiments, the target gas may be, for example, a gas which hasvalue to the user of the membrane and which the user wishes to collect.In alternative embodiments, the target gas may be an undesirable gas,e.g. a pollutant or contaminate, which the user wishes to separate froma gas stream, such as to purify the gas stream or in order to protectthe environment.

In embodiments, membranes comprising porous SOFs may be used forpurifying natural gas (a mixture which predominantly comprises methane)by removing polar gases (CO₂, H₂S); for purifying synthesis gas; and forremoving CO₂ from hydrogen and from flue gases. Flue gases typicallyarise from fireplaces, ovens, furnaces, boilers, combustion engines andpower plants. The composition of flue gases depend on what is beingburned, but usually they contain mostly nitrogen (typically more thantwo-thirds) derived from air, carbon dioxide (CO₂) derived fromcombustion and water vapour as well as oxygen. Flue gases also contain asmall percentage of pollutants such as particulate matter, carbonmonoxide, nitrogen oxides and sulphur oxides.

In embodiments, the methods of separation of the present disclosure,which employ membranes comprising porous SOFs, may be useful forseparating a feed gas comprising a target gas into a product gas streamricher in the target gas than the feed gas and a waste gas stream poorerin target gas than the feed gas (which may be recycled through theseparation process.

In embodiments, the methods of separation of the present disclosure maycomprise measuring adsorption isotherms of one or more of the gases tobe separated and/or stored with various porous SOF compositions. Forexample, for separation of CO₂ from a gaseous mixture, such as anexemplary gaseous mixture comprising CO₂, methane, carbon monoxide andnitrogen, adsorption isotherms may be measured for each of the gaseswith various porous SOF compositions. Then a particular porous SOFcomposition may be selected that has a disproportionately high (or low)affinity and capacity for the desired gas (such as CO₂) to be separatedand/or stored.

In embodiments, a gaseous mixture may be filtered or separated via afiltration/separation column comprising a porous SOF having adisproportionately high affinity and capacity (or a disproportionatelylow affinity and capacity) for a desired gaseous entity. The affinity ofa particular gas for an SOF can be determined by measuring the isostericheat of adsorption at zero coverage as is commonly practiced in the art.For example, such a column may comprise a porous SOF composition capableof separating CO₂ from other gaseous components in a multi-componentgas. In embodiments, such a column may comprise a porous SOF compositioncapable of separating a particular isomer (such as a hydrocarbon isomer(e.g., butane isomers) and/or a xylene isomer) from other gaseouscomponents in a multi-component gas. In embodiments, the porous SOF maybe specifically designed to have a disproportionately high selectivity,affinity and/or capacity for a particular component of a mixture, suchas a gaseous mixture. In embodiments, the porous SOF may be designed tohave a disproportionately high selectivity, affinity and/or capacity foreach component in a mixture other than the desired component of themixture, such as a gaseous mixture.

In embodiments, the porous SOFs of the present disclosure may beincorporated into membranes, such as used in batteries, fuel cells,water purification, etc.). In embodiments, the methods of separation ofthe present disclosure will result in a retentate that may be referredto as being “depleted” of a predetermined component. In embodiments, themethods of separation of the present disclosure will result in effluentstream that may possess the desired product. In embodiments, thisdisclosure provides an apparatus and method for separating one or morecomponents from a multi-component mixtures, such as a gaseous mixture,using a separation system having a feed side and an effluent sideseparated by a porous SOF composition. In embodiments, the porous SOFcomposition may be present in a column.

In embodiments, a gas storage material comprising a porous SOF isprovided. Gases that may be stored or separated by the methods,compositions and systems of the present disclosure include polar gasmolecules, nonpolar gas molecules, and gas molecules comprisingavailable electron density for attachment to the one or more sites. Suchelectron density includes molecules having multiple bonds between twoatoms contained therein or molecules having a lone pair of electrons.Suitable examples of such gases may include the gases comprising acomponent selected from the group consisting of ammonia, argon, carbondioxide, carbon monoxide, hydrogen, and combinations thereof. Inembodiments, the gas binding material comprising a porous SOF possessesbinding sites that may be used to separate the desired gas, such ascarbon dioxide, from a gaseous mixture.

In embodiments, the gaseous storage site comprises a pore in a SOF thatis functionalized with a group having a desired size or charge. Inembodiments, such a group may be a part of the segment and/or linker. Inembodiments, this group may be part of a capped SOF.

In embodiments, the porous SOFs of this disclosure include a pluralityof pores for gas adsorption. In embodiments, the plurality of pores havea unimodal size distribution. In embodiments, the plurality of pores hasa multimodal (e.g., bimodal, trimodal, etc.,) size distribution.

In embodiments, the porous SOFs of the present disclosure may beincorporated into chemical sensors (e.g. resistometric sensors) capableof sensing the presence of an analyte of interest. There is considerableinterest in developing sensors that act as analogs of the mammalianolfactory system. However, may such sensor systems are easilycontaminated. The porous structures of the disclosure provide a definedinteraction area that limits the ability of contaminate to contact asensor material that passes through the porous structure of the SOF.

In embodiments, sensor systems of the present disclosure may includeconductive SOFs, SOFs with conductive regions and non-conductive regionsand non-conductive SOFs. In resistometric systems of the presentdisclosure, conductive leads are separated by the conductive SOFs suchthat a current traverses between the leads and through the sensormaterial. Upon binding to an analyte, the resistance in the materialchanges and detectable signal is thus generated. Using the porous SOFsof the present disclosure, the area surrounding the sensor material islimited and serves as a “filter” to limit contaminants from contactingthe sensor material, which may be an SOF, thus increasing sensorspecificity.

In embodiments, the porous SOF comprises a plurality of segments, aplurality of linkers arranged as a covalent organic framework (COF),such as a “solvent resistant” SOF, a capped SOF, a composite SOF, and/ora periodic SOF. The term “solvent resistant” refers, for example, to thesubstantial absence of (1) any leaching out any atoms and/or moleculesthat were at one time part of the SOF and/or SOF composition (such as acomposite SOF), and/or (2) any phase separation of any molecules thatwere at one time part of the SOF and/or SOF composition (such as acomposite SOF), that increases the susceptibility of the layer intowhich the SOF is incorporated to solvent/stress cracking or degradation.The term “substantial absence” refers for example, to less than about0.5% of the atoms and/or molecules of the SOF being leached out aftercontinuously immersing the SOF in a solvent for a period of about 24hours or longer (such as about 48 hours, or about 72 hours), such asless than about 0.1% of the atoms and/or molecules of the SOF beingleached out after immersing the SOF in a solvent for a period of about24 hours or longer (such as about 48 hours, or about 72 hours), or lessthan about 0.01% of the atoms and/or molecules of the SOF being leachedout after immersing the SOF in a solvent for a period of about 24 hoursor longer (such as about 48 hours, or about 72 hours).

The term “solvent” refers, for example, to organic liquids, aqueousliquids, and/or water.

When a capping unit is introduced into the SOF, the SOF framework islocally ‘interrupted’ where the capping units are present. These SOFcompositions are ‘covalently doped’ because a foreign molecule is bondedto the SOF framework when capping units are present. Capped SOFcompositions may alter the properties of SOFs without changingconstituent building blocks. For example, the mechanical and physicalproperties of the capped SOF where the SOF framework is interrupted maydiffer from that of an uncapped SOF.

The SOFs of the present disclosure may be, at the macroscopic level,substantially pinhole-free SOFs or pinhole-free SOFs having continuouscovalent organic frameworks that can extend over larger length scalessuch as for instance much greater than a millimeter to lengths such as ameter and, in theory, as much as hundreds of meters. It will also beappreciated that SOFs tend to have large aspect ratios where typicallytwo dimensions of a SOF will be much larger than the third. SOFs havemarkedly fewer macroscopic edges and disconnected external surfaces thana collection of COF particles.

In embodiments, a “substantially pinhole-free SOF” or “pinhole-free SOF”may be formed from a reaction mixture deposited on the surface of anunderlying substrate. The term “substantially pinhole-free SOF” refers,for example, to an SOF that may or may not be removed from theunderlying substrate on which it was formed and contains substantiallyno pinholes, pores or gaps greater than the distance between the coresof two adjacent segments per square cm; such as, for example, less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², or less than 5 pinholes, pores or gaps greater than about 100nanometers in diameter per cm². The term “pinhole-free SOF” refers, forexample, to an SOF that may or may not be removed from the underlyingsubstrate on which it was formed and contains no pinholes, pores or gapsgreater than the distance between the cores of two adjacent segments permicron², such as no pinholes, pores or gaps greater than about 500Angstroms in diameter per micron², or no pinholes, pores or gaps greaterthan about 250 Angstroms in diameter per micron², or no pinholes, poresor gaps greater than about 100 Angstroms in diameter per micron².

A description of various exemplary molecular building blocks, segmenttypes, linker types, SOF types, capping groups, strategies to synthesizea specific SOF type with exemplary chemical structures, building blockswhose symmetrical elements are outlined, and classes of exemplarymolecular entities and examples of members of each class that may serveas molecular building blocks for SOFs are detailed in U.S. patentapplication Ser. Nos. 12/716,524; 12/716,449; 12/716,706; 12/716,324;12/716,686; 12/716,571; 12/815,688; 12/845,053; 12/845,235; 12/854,962;12/854,957; and 12/845,052 entitled “Structured Organic Films,”“Structured Organic Films Having an Added Functionality,” “Mixed SolventProcess for Preparing Structured Organic Films,” “Composite StructuredOrganic Films,” “Process For Preparing Structured Organic Films (SOFs)Via a Pre-SOF,” “Electronic Devices Comprising Structured OrganicFilms,” “Periodic Structured Organic Films,” “Capped Structured OrganicFilm Compositions,” “Imaging Members Comprising Capped StructuredOrganic Film Compositions,” “Imaging Members for Ink-Based DigitalPrinting Comprising Structured Organic Films,” “Imaging DevicesComprising Structured Organic Films,” and “Imaging Members ComprisingStructured Organic Films,” respectively; and U.S. ProvisionalApplication No. 61/157,411, entitled “Structured Organic Films” filedMar. 4, 2009, the disclosures of which are totally incorporated hereinby reference in their entireties.

Molecular Building Block

The SOFs of the present disclosure comprise molecular building blockshaving a segment (S) and functional groups (Fg). Molecular buildingblocks require at least two functional groups (x≧2) and may comprise asingle type or two or more types of functional groups. Functional groupsare the reactive chemical moieties of molecular building blocks thatparticipate in a chemical reaction to link together segments during theSOF forming process. A segment is the portion of the molecular buildingblock that supports functional groups and comprises all atoms that arenot associated with functional groups. Further, the composition of amolecular building block segment remains unchanged after SOF formation.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

FIGS. 1A-O illustrate exemplary building blocks whose symmetricalelements are outlined. Such symmetrical elements are found in buildingblocks that may be used in the present disclosure.

Non-limiting examples of various classes of exemplary molecular entitiesthat may serve as molecular building blocks for SOFs of the presentdisclosure include building blocks containing a carbon or silicon atomiccore; building blocks containing alkoxy cores; building blockscontaining a nitrogen or phosphorous atomic core; building blockscontaining aryl cores; building blocks containing carbonate cores;building blocks containing carbocyclic-, carbobicyclic-, orcarbotricyclic core; and building blocks containing an oligothiophenecore. Incorporation of one or more of the above molecular buildingblocks in the porous SOF reaction mixture may result in a porous SOFwith a plurality of segments having one or more cores selected from thegroup consisting of carbon, nitrogen, silicon, or phosphorous atomiccores, alkyl cores, fluoroalkyl cores, alkoxy cores, aryl cores,carbonate cores, carbocyclic cores, carbobicyclic cores, carbotricycliccores, and oligothiophene cores, respectively.

In embodiments, the Type 1 SOF contains segments, which are not locatedat the edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Functional Group

Functional groups are the reactive chemical moieties of molecularbuilding blocks that participate in a chemical reaction to link togethersegments during the SOF forming process. Functional groups may becomposed of a single atom, or functional groups may be composed of morethan one atom. The atomic compositions of functional groups are thosecompositions normally associated with reactive moieties in chemicalcompounds. Non-limiting examples of functional groups include halogens,alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines,amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes,alkynes and the like.

Molecular building blocks contain a plurality of chemical moieties, butonly a subset of these chemical moieties are intended to be functionalgroups during the SOF forming process. Whether or not a chemical moietyis considered a functional group depends on the reaction conditionsselected for the SOF forming process. Functional groups (Fg) denote achemical moiety that is a reactive moiety, that is, a functional groupduring the SOF forming process.

In the SOF forming process, the composition of a functional group willbe altered through the loss of atoms, the gain of atoms, or both theloss and the gain of atoms; or, the functional group may be lostaltogether. In the SOF, atoms previously associated with functionalgroups become associated with linker groups, which are the chemicalmoieties that join together segments. Functional groups havecharacteristic chemistries and those of ordinary skill in the art cangenerally recognize in the present molecular building blocks the atom(s)that constitute functional group(s). It should be noted that an atom orgrouping of atoms that are identified as part of the molecular buildingblock functional group may be preserved in the linker group of the SOF.Linker groups are described below.

Capping Unit

Capping units of the present disclosure are molecules that ‘interrupt’the regular network of covalently bonded building blocks normallypresent in an SOF. Capped SOF compositions are tunable materials whoseproperties can be varied through the type and amount of capping unitintroduced. Capping units may comprise a single type or two or moretypes of functional groups and/or chemical moieties.

In embodiments, the SOF comprises a plurality of segments, where allsegments have an identical structure, and a plurality of linkers, whichmay or may not have an identical structure, wherein the segments thatare not at the edges of the SOF are connected by linkers to at leastthree other segments and/or capping groups. In embodiments, the SOFcomprises a plurality of segments where the plurality of segmentscomprises at least a first and a second segment that are different instructure, and the first segment is connected by linkers to at leastthree other segments and/or capping groups when it is not at the edge ofthe SOF.

In embodiments, the SOF comprises a plurality of linkers including atleast a first and a second linker that are different in structure, andthe plurality of segments either comprises at least a first and a secondsegment that are different in structure, where the first segment, whennot at the edge of the SOF, is connected to at least three othersegments and/or capping groups, wherein at least one of the connectionsis via the first linker, and at least one of the connections is via thesecond linker; or comprises segments that all have an identicalstructure, and the segments that are not at the edges of the SOF areconnected by linkers to at least three other segments and/or cappinggroups, wherein at least one of the connections is via the first linker,and at least one of the connections is via the second linker.

Segment

A segment is the portion of the molecular building block that supportsfunctional groups and comprises all atoms that are not associated withfunctional groups. Further, the composition of a molecular buildingblock segment remains unchanged after SOF formation. In embodiments, theSOF may contain a first segment having a structure the same as ordifferent from a second segment. In other embodiments, the structures ofthe first and/or second segments may be the same as or different from athird segment, forth segment, fifth segment, etc. A segment is also theportion of the molecular building block that can provide an inclinedproperty. Inclined properties are described later in the embodiments.

The SOF of the present disclosure comprise a plurality of segmentsincluding at least a first segment type and a plurality of linkersincluding at least a first linker type arranged as a covalent organicframework (COF) having a plurality of pores, wherein the first segmenttype and/or the first linker type comprises at least one atom that isnot carbon. In embodiments, the segment (or one or more of the pluralityof segments) of the SOF comprises at least one atom of an element thatis not carbon, such as where the structure of the segment comprises atleast one atom selected from the group consisting of hydrogen, oxygen,nitrogen, silicon, phosphorous, selenium, fluorine, boron, and sulfur.

Linker

A linker is a chemical moiety that emerges in a SOF upon chemicalreaction between functional groups present on the molecular buildingblocks and/or capping unit.

A linker may comprise a covalent bond, a single atom, or a group ofcovalently bonded atoms. The former is defined as a covalent bond linkerand may be, for example, a single covalent bond or a double covalentbond and emerges when functional groups on all partnered building blocksare lost entirely. The latter linker type is defined as a chemicalmoiety linker and may comprise one or more atoms bonded together bysingle covalent bonds, double covalent bonds, or combinations of thetwo. Atoms contained in linking groups originate from atoms present infunctional groups on molecular building blocks prior to the SOF formingprocess. Chemical moiety linkers may be well-known chemical groups suchas, for example, esters, ketones, amides, imines, ethers, urethanes,carbonates, and the like, or derivatives thereof. In embodiments, porousSOF having a plurality of linkers my comprise one or more linkersselected from the group consisting of single atom linkers, singlecovalent bond linkers, and double covalent bond linkers, ester linkers,ketone linkers, amide linkers, amine linkers, imine linkers, etherlinkers, urethane linkers, and carbonates linkers.

For example, when two hydroxyl (—OH) functional groups are used toconnect segments in a SOF via an oxygen atom, the linker would be theoxygen atom, which may also be described as an ether linker. Inembodiments, the SOF may contain a first linker having a structure thesame as or different from a second linker. In other embodiments, thestructures of the first and/or second linkers may be the same as ordifferent from a third linker, etc.

The SOF of the present disclosure comprise a plurality of segmentsincluding at least a first segment type and a plurality of linkersincluding at least a first linker type arranged as a covalent organicframework (COF) having a plurality of pores, wherein the first segmenttype and/or the first linker type comprises at least one atom that isnot carbon. In embodiments, the linker (or one or more of the pluralityof linkers) of the SOF comprises at least one atom of an element that isnot carbon, such as where the structure of the linker comprises at leastone atom selected from the group consisting of hydrogen, oxygen,nitrogen, silicon, phosphorous, selenium, fluorine, boron, and sulfur.

Metrical Parameters of SOFs

SOFs have any suitable aspect ratio. In embodiments, SOFs have aspectratios for instance greater than about 30:1 or greater than about 50:1,or greater than about 70:1, or greater than about 100:1, such as about1000:1. The aspect ratio of a SOF is defined as the ratio of its averagewidth or diameter (that is, the dimension next largest to its thickness)to its average thickness (that is, its shortest dimension). The term‘aspect ratio,’ as used here, is not bound by theory. The longestdimension of a SOF is its length and it is not considered in thecalculation of SOF aspect ratio.

Multilayer SOFs

A SOF may comprise a single layer or a plurality of layers (that is,two, three or more layers). SOFs that are comprised of a plurality oflayers may be physically joined (e.g., dipole and hydrogen bond) orchemically joined. Physically attached layers are characterized byweaker interlayer interactions or adhesion; therefore physicallyattached layers may be susceptible to delamination from each other.Chemically attached layers are expected to have chemical bonds (e.g.,covalent or ionic bonds) or have numerous physical or intermolecular(supramolecular) entanglements that strongly link adjacent layers.

Therefore, delamination of chemically attached layers is much moredifficult. Chemical attachments between layers may be detected usingspectroscopic methods such as focusing infrared or Raman spectroscopy,or with other methods having spatial resolution that can detect chemicalspecies precisely at interfaces. In cases where chemical attachmentsbetween layers are different chemical species than those within thelayers themselves it is possible to detect these attachments withsensitive bulk analyses such as solid-state nuclear magnetic resonancespectroscopy or by using other bulk analytical methods.

In the embodiments, the coating may comprise a SOF where the SOF may bea single layer (mono-segment thick or multi-segment thick) or multiplelayers (each layer being mono-segment thick or multi-segment thick).“Thickness” refers, for example, to the smallest dimension of the film.As discussed above, in a SOF, segments are molecular units that arecovalently bonded through linkers to generate the molecular framework ofthe film. The thickness of the film may also be defined in terms of thenumber of segments that is counted along that axis of the film whenviewing the cross-section of the film. A “monolayer” SOF is the simplestcase and refers, for example, to where a film is one segment thick. ASOF where two or more segments exist along this axis is referred to as a“multi-segment” thick SOF.

An exemplary method for preparing a physically attached multilayerporous SOF includes: (1) forming a base SOF layer that may be cured by afirst curing cycle, and (2) forming upon the base layer a secondreactive wet layer followed by a second curing cycle and, if desired,repeating the second step to form a third layer, a forth layer and soon. The physically stacked multilayer SOFs may have thicknesses greaterthan about 20 Angstroms such as, for example, the following illustrativethicknesses: about 20 Angstroms to about 10 cm, such as about 1 nm toabout 10 mm, or about 0.1 mm Angstroms to about 5 mm. In principle thereis no limit with this process to the number of layers that may bephysically stacked.

In embodiments, a multilayer porous SOF may be formed by a method forpreparing chemically attached multilayer SOFs by: (1) forming a base SOFlayer having functional groups present on the surface (or danglingfunctional groups) from a first reactive wet layer, and (2) forming uponthe base layer a second SOF layer from a second reactive wet layer thatcomprises molecular building blocks with functional groups capable ofreacting with the dangling functional groups on the surface of the baseSOF layer. In further embodiments, a capped SOF may serve as the baselayer in which the functional groups present that were not suitable orcomplementary to participate in the specific chemical reaction to linktogether segments during the base layer SOF forming process may beavailable for reacting with the molecular building blocks of the secondlayer to from an chemically bonded multilayer SOF. If desired, theformulation used to form the second SOF layer should comprise molecularbuilding blocks with functional groups capable of reacting with thefunctional groups from the base layer as well as additional functionalgroups that will allow for a third layer to be chemically attached tothe second layer. The chemically stacked multilayer SOFs may havethicknesses greater than about 20 Angstroms such as, for example, thefollowing illustrative thicknesses: about 20 Angstroms to about 10 cm,such as about 1 nm to about 10 mm, or about 0.1 mm Angstroms to about 5mm. In principle there is no limit with this process to the number oflayers that may be chemically stacked.

In embodiments, the method for preparing chemically attached multilayerSOFs comprises promoting chemical attachment of a second SOF onto anexisting SOF (base layer) by using a small excess of one molecularbuilding block (when more than one molecular building block is present)during the process used to form the SOF (base layer) whereby thefunctional groups present on this molecular building block will bepresent on the base layer surface. The surface of base layer may betreated with an agent to enhance the reactivity of the functional groupsor to create an increased number of functional groups.

In an embodiment the dangling functional groups or chemical moietiespresent on the surface of an SOF or capped SOF may be altered toincrease the propensity for covalent attachment (or, alternatively, todisfavor covalent attachment) of particular classes of molecules orindividual molecules, such as SOFs, to a base layer or any additionalsubstrate or SOF layer. For example, the surface of a base layer, suchas an SOF layer, which may contain reactive dangling functional groups,may be rendered pacified through surface treatment with a cappingchemical group. For example, a SOF layer having dangling hydroxylalcohol groups may be pacified by treatment with trimethylsiylchloridethereby capping hydroxyl groups as stable trimethylsilylethers.Alternatively, the surface of base layer may be treated with anon-chemically bonding agent, such as a wax, to block reaction withdangling functional groups from subsequent layers.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

In embodiments, a Type 1 SOF contains segments, which are not located atthe edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Practice of Linking Chemistry

In embodiments linking chemistry may occur wherein the reaction betweenfunctional groups produces a volatile byproduct that may be largelyevaporated or expunged from the SOF during or after the film formingprocess or wherein no byproduct is formed. Linking chemistry may beselected to achieve a SOF for applications where the presence of linkingchemistry byproducts is not desired. Linking chemistry reactions mayinclude, for example, condensation, addition/elimination, and additionreactions, such as, for example, those that produce esters, imines,ethers, carbonates, urethanes, amides, acetals, and silyl ethers.

In embodiments the linking chemistry via a reaction between functiongroups producing a non-volatile byproduct that largely remainsincorporated within the SOF after the film forming process. Linkingchemistry in embodiments may be selected to achieve a SOF forapplications where the presence of linking chemistry byproducts does notimpact the properties or for applications where the presence of linkingchemistry byproducts may alter the properties of a SOF (such as, forexample, the electroactive, hydrophobic or hydrophilic nature of theSOF). Linking chemistry reactions may include, for example,substitution, metathesis, and metal catalyzed coupling reactions, suchas those that produce carbon-carbon bonds.

For all linking chemistry the ability to control the rate and extent ofreaction between building blocks via the chemistry between buildingblock functional groups is an important aspect of the presentdisclosure. Reasons for controlling the rate and extent of reaction mayinclude adapting the film forming process for different coating methodsand tuning the microscopic arrangement of building blocks to achieve aperiodic SOF, as defined in earlier embodiments.

Innate Properties of COFs

COFs have innate properties such as high thermal stability (typicallyhigher than 400° C. under atmospheric conditions); poor solubility inorganic solvents (chemical stability), and porosity (capable ofreversible guest uptake). In embodiments, SOFs may also possess theseinnate properties.

Added Functionality of SOFs

Added functionality denotes a property that is not inherent toconventional COFs and may occur by the selection of molecular buildingblocks wherein the molecular compositions provide the addedfunctionality in the resultant SOF. Added functionality may arise uponassembly of molecular building blocks having an “inclined property” forthat added functionality. Added functionality may also arise uponassembly of molecular building blocks having no “inclined property” forthat added functionality but the resulting SOF has the addedfunctionality as a consequence of linking segments (S) and linkers intoa SOF. Furthermore, emergence of added functionality may arise from thecombined effect of using molecular building blocks bearing an “inclinedproperty” for that added functionality whose inclined property ismodified or enhanced upon linking together the segments and linkers intoa SOF.

An Inclined Property of a Molecular Building Block

The term “inclined property” of a molecular building block refers, forexample, to a property known to exist for certain molecular compositionsor a property that is reasonably identifiable by a person skilled in artupon inspection of the molecular composition of a segment. As usedherein, the terms “inclined property” and “added functionality” refer tothe same general property (e.g., hydrophobic, electroactive, etc.) but“inclined property” is used in the context of the molecular buildingblock and “added functionality” is used in the context of the SOF.

The hydrophobic (superhydrophobic), hydrophilic, lipophobic(superlipophobic), lipophilic, photochromic and/or electroactive(conductor, semiconductor, charge transport material) nature of an SOFare some examples of the properties that may represent an “addedfunctionality” of an SOF. These and other added functionalities mayarise from the inclined properties of the molecular building blocks ormay arise from building blocks that do not have the respective addedfunctionality that is observed in the SOF.

The term hydrophobic (superhydrophobic) refers, for example, to theproperty of repelling water, or other polar species, such as methanol,it also means an inability to absorb water and/or to swell as a result.Furthermore, hydrophobic implies an inability to form strong hydrogenbonds to water or other hydrogen bonding species. Hydrophobic materialsare typically characterized by having water contact angles greater than90° as measured using a contact angle goniometer or related device.Highly hydrophobic as used herein can be described as when a droplet ofwater forms a high contact angle with a surface, such as a contact angleof from about 130° to about 180°. Superhydrophobic as used herein can bedescribed as when a droplet of water forms a high contact angle with asurface, such as a contact angle of greater than about 150°, or fromgreater about 150° to about 180°.

Superhydrophobic as used herein can be described as when a droplet ofwater forms a sliding angle with a surface, such as a sliding angle offrom about 1° to less than about 30°, or from about 1° to about 25°, ora sliding angle of less than about 15°, or a sliding angle of less thanabout 10°.

The term hydrophilic refers, for example, to the property of attracting,adsorbing, or absorbing water or other polar species, or a surface thatis easily wetted by such species. Hydrophilic materials are typicallycharacterized by having less than 20° water contact angle as measuredusing a contact angle goniometer or related device. Hydrophilicity mayalso be characterized by swelling of a material by water or other polarspecies, or a material that can diffuse or transport water, or otherpolar species, through itself. Hydrophilicity, is further characterizedby being able to form strong or numerous hydrogen bonds to water orother hydrogen bonding species.

The term lipophobic (oleophobic) refers, for example, to the property ofrepelling oil or other non-polar species such as alkanes, fats, andwaxes. Lipophobic materials are typically characterized by having oilcontact angles greater than 90° as measured using a contact anglegoniometer or related device. In the present disclosure, the termoleophobic refers, for example, to wettability of a surface that has anoil contact angle of approximately about 55° or greater, for example,with UV gel ink, solid ink, hexadecane, dodecane, hydrocarbons, etc.Highly oleophobic as used herein can be described as when a droplet ofhydrocarbon-based liquid, for example, hexadecane or ink, forms a highcontact angle with a surface, such as a contact angle of from about 130°or greater than about 130° to about 175° or from about 135° P about170°. Superoleophobic as used herein can be described as when a dropletof hydrocarbon-based liquid, for example, ink, forms a highcontact-angle with a surface, such as a contact angle that is greaterthan 150°, or from greater than about 150° to about 175°, or fromgreater than about 150° to about 160°.

Superoleophobic as used herein can also be described as when a dropletof a hydrocarbon-based liquid, for example, hexadecane, forms a slidingangle with a surface of from about 1° to less than about 30°, or fromabout 1° to less than about 25°, or a sliding angle of less than about25°, or a sliding angle of less than about 15°, or a sliding angle ofless than about 10°.

The term lipophilic (oleophilic) refers, for example, to the propertyattracting oil or other non-polar species such as alkanes, fats, andwaxes or a surface that is easily wetted by such species. Lipophilicmaterials are typically characterized by having a low to nil oil contactangle as measured using, for example, a contact angle goniometer.Lipophilicity can also be characterized by swelling of a material byhexane or other non-polar liquids.

The term photochromic refers, for example, to the ability to demonstratereversible color changes when exposed to electromagnetic radiation. SOFcompositions containing photochromic molecules may be prepared anddemonstrate reversible color changes when exposed to electromagneticradiation. These SOFs may have the added functionality of photochromism.The robustness of photochromic SOFs may enable their use in manyapplications, such as photochromic SOFs for erasable paper, and lightresponsive films for window tinting/shading and eye wear. SOFcompositions may contain any suitable photochromic molecule, such as adifunctional photochromic molecules as SOF molecular building blocks(chemically bound into SOF structure), a monofunctional photochromicmolecules as SOF capping units (chemically bound into SOF structure, orunfunctionalized photochromic molecules in an SOF composite (notchemically bound into SOF structure). Photochromic SOFs may change colorupon exposure to selected wavelengths of light and the color change maybe reversible.

SOF compositions containing photochromic molecules that chemically bondto the SOF structure are exceptionally chemically and mechanicallyrobust photochromic materials. Such photochromic SOF materialsdemonstrate many superior properties, such as high number of reversiblecolor change processes, to available polymeric alternatives.

The term electroactive refers, for example, to the property to transportelectrical charge (electrons and/or holes). Electroactive materialsinclude conductors, semiconductors, and charge transport materials.Conductors are defined as materials that readily transport electricalcharge in the presence of a potential difference. Semiconductors aredefined as materials do not inherently conduct charge but may becomeconductive in the presence of a potential difference and an appliedstimuli, such as, for example, an electric field, electromagneticradiation, heat, and the like. Charge transport materials are defined asmaterials that can transport charge when charge is injected from anothermaterial such as, for example, a dye, pigment, or metal in the presenceof a potential difference.

Conductors may be further defined as materials that give a signal usinga potentiometer from about 0.1 to about 10⁷ S/cm.

Semiconductors may be further defined as materials that give a signalusing a potentiometer from about 10⁻⁶ to about 10⁴ S/cm in the presenceof applied stimuli such as, for example an electric field,electromagnetic radiation, heat, and the like. Alternatively,semiconductors may be defined as materials having electron and/or holemobility measured using time-of-flight techniques in the range of 10⁻¹⁰to about 10⁶ cm²V⁻¹s⁻¹ when exposed to applied stimuli such as, forexample an electric field, electromagnetic radiation, heat, and thelike.

Charge transport materials may be further defined as materials that haveelectron and/or hole mobility measured using time-of-flight techniquesin the range of 10⁻¹⁰ to about 10⁶ cm²V⁻¹s⁻¹. It should be noted thatunder some circumstances charge transport materials may be alsoclassified as semiconductors.

SOFs with hydrophobic added functionality may be prepared by usingmolecular building blocks with inclined hydrophobic properties and/orhave a rough, textured, or porous surface on the sub-micron to micronscale. A paper describing materials having a rough, textured, or poroussurface on the sub-micron to micron scale being hydrophobic was authoredby Cassie and Baxter (Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc.,1944, 40, 546).

Molecular building blocks comprising or bearing highly-fluorinatedsegments have inclined hydrophobic properties and may lead to SOFs withhydrophobic added functionality. Highly-fluorinated segments are definedas the number of fluorine atoms present on the segment(s) divided by thenumber of hydrogen atoms present on the segment(s) being greater thanone. Fluorinated segments, which are not highly-fluorinated segments mayalso lead to SOFs with hydrophobic added functionality.

The above-mentioned fluorinated segments may include, for example,tetrafluorohydroquinone, perfluoroadipic acid hydrate,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphenol, and the like. Other exemplaryfluorinated SOFs are described in U.S. patent application Ser. No.13/173,948, to Adrien P. Cote and Matthew A. Heuft entitled “FluorinatedStructured Organic Film Compositions,” the disclosure of which istotally incorporated herein by reference in its entirety.

SOFs having a rough, textured, or porous surface on the sub-micron tomicron scale may also be hydrophobic. The rough, textured, or porous SOFsurface can result from dangling functional groups present on the filmsurface or from the structure of the SOF. The type of pattern and degreeof patterning depends on the geometry of the molecular building blocksand the linking chemistry efficiency. The feature size that leads tosurface roughness or texture is from about 100 nm to about 10 μm, suchas from about 500 nm to about 5 μm.

SOFs with hydrophilic added functionality may be prepared by usingmolecular building blocks with inclined hydrophilic properties and/orcomprising polar linking groups.

Molecular building blocks comprising segments bearing polar substituentshave inclined hydrophilic properties and may lead to SOFs withhydrophilic added functionality. The term polar substituents refers, forexample, to substituents that can form hydrogen bonds with water andinclude, for example, hydroxyl, amino, ammonium, and carbonyl (such asketone, carboxylic acid, ester, amide, carbonate, urea).

SOFs with electroactive added functionality may be prepared by usingmolecular building blocks with inclined electroactive properties and/orbe electroactive resulting from the assembly of conjugated segments andlinkers. The following sections describe molecular building blocks withinclined hole transport properties, inclined electron transportproperties, and inclined semiconductor properties.

Process for Preparing a Structured Organic Film

The process for making porous SOFs of the present disclosure, such assolvent resistant porous SOFs, typically comprises a number ofactivities or steps (set forth below) that may be performed in anysuitable sequence or where two or more activities are performedsimultaneously or in close proximity in time:

A process for preparing a structured organic film comprising:

(a) preparing a liquid-containing reaction mixture comprising aplurality of molecular building blocks each comprising a segment and anumber of functional groups, and a pre-SOF;

(b) depositing the reaction mixture as a wet film;

(c) promoting a change of the wet film including the molecular buildingblocks to a dry film comprising the SOF (dry SOF) comprising a pluralityof the segments and a plurality of linkers arranged as a covalentorganic framework, wherein at a macroscopic level the covalent organicframework is a film;

(d) optionally removing the SOF from the coating substrate to obtain afree-standing SOF;

(e) optionally processing the free-standing SOF into a roll;

(f) optionally cutting and seaming the SOF into a belt;

(g) optionally performing the above SOF formation process(es) upon anSOF (which was prepared by the above SOF formation process(es)) as asubstrate for subsequent SOF formation process(es); and

(h) optionally activating the above dry SOF in order empty the pluralityof pores and remove any residual chemical species that may remain afterformation of the SOF.

The process for making capped SOFs and/or composite SOFs typicallycomprises a similar number of activities or steps (set forth above) thatare used to make a non-capped SOF. The capping unit and/or secondarycomponent may be added during either step a, b or c, depending thedesired distribution of the capping unit in the resulting SOF. Forexample, if it is desired that the capping unit and/or secondarycomponent distribution is substantially uniform over the resulting SOF,the capping unit may be added during step a. Alternatively, if, forexample, a more heterogeneous distribution of the capping unit and/orsecondary component is desired, adding the capping unit and/or secondarycomponent (such as by spraying it on the film formed during step b orduring the promotion step of step e) may occur during steps b and e.

The above activities or steps may be conducted at atmospheric, superatmospheric, or subatmospheric pressure. The term “atmospheric pressure”as used herein refers to a pressure of about 760 torr. The term “superatmospheric” refers to pressures greater than atmospheric pressure, butless than 20 atm. The term “subatmospheric pressure” refers to pressuresless than atmospheric pressure. In an embodiment, the activities orsteps may be conducted at or near atmospheric pressure. Generally,pressures of from about 0.1 atm to about 2 atm, such as from about 0.5atm to about 1.5 atm, or 0.8 atm to about 1.2 atm may be convenientlyemployed.

Process Action A: Preparation of the Liquid-Containing Reaction Mixture

The reaction mixture comprises a plurality of molecular building blocksthat are dissolved, suspended, or mixed in a liquid. The plurality ofmolecular building blocks may be of one type or two or more types. Whenone or more of the molecular building blocks is a liquid, the use of anadditional liquid is optional. Catalysts may optionally be added to thereaction mixture to enable pre-SOF formation and/or modify the kineticsof SOF formation during Action C described above. The term “pre-SOF” mayrefer to, for example, at least two molecular building blocks that havereacted and have a molecular weight higher than the starting molecularbuilding block and contain multiple functional groups capable ofundergoing further reactions with functional groups of other buildingblocks or pre-SOFs to obtain a SOF, which may be a substantiallydefect-free or defect-free SOF, and/or the ‘activation’ of molecularbuilding block functional groups that imparts enhanced or modifiedreactivity for the film forming process. Activation may includedissociation of a functional group moiety, pre-association with acatalyst, association with a solvent molecule, liquid, second solvent,second liquid, secondary component, or with any entity that modifiesfunctional group reactivity. In embodiments, pre-SOF formation mayinclude the reaction between molecular building blocks or the‘activation’ of molecular building block functional groups, or acombination of the two. The formation of the “pre-SOF” may be achievedby in a number of ways, such as heating the reaction mixture, exposureof the reaction mixture to UV radiation, or any other means of partiallyreacting the molecular building blocks and/or activating functionalgroups in the reaction mixture prior to deposition of the wet layer onthe substrate. Additives or secondary components may optionally be addedto the reaction mixture to alter the physical properties of theresulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically when a process for preparing a SOF includes apre-SOF or formation of a pre-SOF, the catalyst, when present, may beadded to the reaction mixture before depositing the reaction mixture asa wet film. In embodiments, the molecular building blocks may be reactedactinically, thermally, chemically or by any other means with or withoutthe presence of a catalyst to obtain a pre-SOF. The pre-SOF and themolecular building blocks formed in the absence of catalyst may be maybe heated in the liquid in the absence of the catalyst to aid thedissolution of the molecular building blocks and pre-SOFs. Inembodiments, the pre-SOF and the molecular building blocks formed in thepresence of catalyst may be may be heated at a temperature that does notcause significant further reaction of the molecular building blocksand/or the pre-SOFs to aid the dissolution of the molecular buildingblocks and pre-SOFs. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer to form pre-SOFs. For example, the weightpercent of molecular building blocks in the reaction mixture that areincorporated into pre-reacted molecular building blocks pre-SOFs may beless than 20%, such as about 15% to about 1%, or 10% to about 5%. Inembodiments, the molecular weight of the 95% pre-SOF molecules is lessthan 5,000 daltons, such as 2,500 daltons, or 1,000 daltons. Thepreparation of pre-SOFs may be used to increase the loading of themolecular building blocks in the reaction mixture.

In the case of pre-SOF formation via functional group activation, themolar percentage of functional groups that are activated may be lessthan 50%, such as about 30% to about 10%, or about 10% to about 5%.

In embodiments, the two methods of pre-SOF formation (pre-SOF formationby the reaction between molecular building blocks or pre-SOF formationby the ‘activation’ of molecular building block functional groups) mayoccur in combination and the molecular building blocks incorporated intopre-SOF structures may contain activated functional groups. Inembodiments, pre-SOF formation by the reaction between molecularbuilding blocks and pre-SOF formation by the ‘activation’ of molecularbuilding block functional groups may occur simultaneously.

In embodiments, the duration of pre-SOF formation lasts about 10 secondsto about 48 hours, such as about 30 seconds to about 12 hours, or about1 minute to 6 hours.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block and capping unit loading or “loading” inthe reaction mixture is defined as the total weight of the molecularbuilding blocks and optionally the capping units and catalysts dividedby the total weight of the reaction mixture. Building block loadings mayrange from about 3 to 100%, such as from about 5 to about 50%, or fromabout 15 to about 40%. In the case where a liquid molecular buildingblock is used as the only liquid component of the reaction mixture (i.e.no additional liquid is used), the building block loading would be about100%. The capping unit loading may be chosen, so as to achieve thedesired loading of the capping group. For example, depending on when thecapping unit is to be added to the reaction mixture, capping unitloadings may range, by weight, from about 3 to 80%, such as from about 5to about 50%, or from about 15 to about 40% by weight.

In embodiments, the theoretical upper limit for capping unit loading isthe molar amount of capping units that reduces the number of availablelinking groups to 2 per molecular building block in the liquid SOFformulation. In such a loading, substantial SOF formation may beeffectively inhibited by exhausting (by reaction with the respectivecapping group) the number of available linkable functional groups permolecular building block. For example, in such a situation (where thecapping unit loading is in an amount sufficient to ensure that the molarexcess of available linking groups is less than 2 per molecular buildingblock in the liquid SOF formulation), oligomers, linear polymers, andmolecular building blocks that are fully capped with capping units maypredominately form instead of an SOF.

In embodiments, the pre-SOF may be made from building blocks with one ormore of the added functionality selected from the group consisting ofhydrophobic added functionality, superhydrophobic added functionality,hydrophilic added functionality, lipophobic added functionality,superlipophobic added functionality, lipophilic added functionality,photochromic added functionality, and electroactive added functionality.In embodiments, the inclined property of the molecular building blocksis the same as the added functionality of the pre-SOF. In embodiments,the added functionality of the SOF is not an inclined property of themolecular building blocks.

Liquids used in the reaction mixture may be pure liquids, such assolvents, and/or solvent mixtures. Liquids are used to dissolve orsuspend the molecular building blocks and catalyst/modifiers in thereaction mixture. Liquid selection is generally based on balancing thesolubility/dispersion of the molecular building blocks and a particularbuilding block loading, the viscosity of the reaction mixture, and theboiling point of the liquid, which impacts the promotion of the wetlayer to the dry SOF. Suitable liquids may have boiling points fromabout 30 to about 300° C., such as from about 65° C. to about 250° C.,or from about 100° C. to about 180° C.

Liquids may include molecule classes such as alkanes (hexane, heptane,octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane,decalin); mixed alkanes (hexanes, heptanes); branched alkanes(isooctane); aromatic compounds (toluene, o-, p-xylene, mesitylene,nitrobenzene, benzonitrile, butylbenzene, aniline); ethers (benzyl ethylether, butyl ether, isoamyl ether, propyl ether); cyclic ethers(tetrahydrofuran, dioxane), esters (ethyl acetate, butyl acetate, butylbutyrate, ethoxyethyl acetate, ethyl propionate, phenyl acetate, methylbenzoate); ketones (acetone, methyl ethyl ketone, methyl isobutylketone,diethyl ketone, chloroacetone, 2-heptanone), cyclic ketones(cyclopentanone, cyclohexanone), amines (1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine;pyridine); amides (dimethylformamide, N-methylpyrolidinoneN,N-dimethylformamide); alcohols (methanol, ethanol, n-, i-propanol, n-,t-butanol, 1-methoxy-2-propanol, hexanol, cyclohexanol, 3-pentanol,benzyl alcohol); nitriles (acetonitrile, benzonitrile, butyronitrile),halogenated aromatics (chlorobenzene, dichlorobenzene,hexafluorobenzene), halogenated alkanes (dichloromethane, chloroform,dichloroethylene, tetrachloroethane); and water.

Mixed liquids comprising a first solvent, second solvent, third solvent,and so forth may also be used in the reaction mixture. Two or moreliquids may be used to aid the dissolution/dispersion of the molecularbuilding blocks; and/or increase the molecular building block loading;and/or allow a stable wet film to be deposited by aiding the wetting ofthe substrate and deposition instrument; and/or modulate the promotionof the wet layer to the dry SOF. In embodiments, the second solvent is asolvent whose boiling point or vapor-pressure curve or affinity for themolecular building blocks differs from that of the first solvent. Inembodiments, a first solvent has a boiling point higher than that of thesecond solvent. In embodiments, the second solvent has a boiling pointequal to or less than about 100° C., such as in the range of from about30° C. to about 100° C., or in the range of from about 40° C. to about90° C., or about 50° C. to about 80° C.

In embodiments, the first solvent, or higher boiling point solvent, hasa boiling point equal to or greater than about 65° C., such as in therange of from about 80° C. to about 300° C., or in the range of fromabout 100° C. to about 250° C., or about 100° C. to about 180° C. Thehigher boiling point solvent may include, for example, the following(the value in parentheses is the boiling point of the compound):hydrocarbon solvents such as amylbenzene (202° C.), isopropylbenzene(152° C.), 1,2-diethylbenzene (183° C.), 1,3-diethylbenzene (181° C.),1,4-diethylbenzene (184° C.), cyclohexylbenzene (239° C.), dipentene(177° C.), 2,6-dimethylnaphthalene (262° C.), p-cymene (177° C.),camphor oil (160-185° C.), solvent naphtha (110-200° C.), cis-decalin(196° C.), trans-decalin (187° C.), decane (174° C.), tetralin (207°C.), turpentine oil (153-175° C.), kerosene (200-245° C.), dodecane(216° C.), dodecylbenzene (branched), and so forth; ketone and aldehydesolvents such as acetophenone (201.7° C.), isophorone (215.3° C.),phorone (198-199° C.), methylcyclohexanone (169.0-170.5° C.), methyln-heptyl ketone (195.3° C.), and so forth; ester solvents such asdiethyl phthalate (296.1° C.), benzyl acetate (215.5° C.),y-butyrolactone (204° C.), dibutyl oxalate (240° C.), 2-ethylhexylacetate (198.6° C.), ethyl benzoate (213.2° C.), benzyl formate (203°C.), and so forth; diethyl sulfate (208° C.), sulfolane (285° C.), andhalohydrocarbon solvents; etherified hydrocarbon solvents; alcoholsolvents; ether/acetal solvents; polyhydric alcohol solvents; carboxylicanhydride solvents; phenolic solvents; water; and silicone solvents.

The ratio of the mixed liquids may be established by one skilled in theart. The ratio of liquids a binary mixed liquid may be from about 1:1 toabout 99:1, such as from about 1:10 to about 10:1, or about 1:5 to about5:1, by volume. When n liquids are used, with n ranging from about 3 toabout 6, the amount of each liquid ranges from about 1% to about 95%such that the sum of each liquid contribution equals 100%.

In embodiments, the mixed liquid comprises at least a first and a secondsolvent with different boiling points. In further embodiments, thedifference in boiling point between the first and the second solvent maybe from about nil to about 150° C., such as from nil to about 50° C. Forexample, the boiling point of the first solvent may exceed the boilingpoint of the second solvent by about 1° C. to about 100° C., such as byabout 5° C. to about 100° C., or by about 10° C. to about 50° C. Themixed liquid may comprise at least a first and a second solvent withdifferent vapor pressures, such as combinations of high vapor pressuresolvents and/or low vapor pressure solvents. The term “high vaporpressure solvent” refers to, for example, a solvent having a vaporpressure of at least about 1 kPa, such as about 2 kPa, or about 5 kPa.The term “low vapor pressure solvent” refers to, for example, a solventhaving a vapor pressure of less than about 1 kPa, such as about 0.9 kPa,or about 0.5 kPa. In embodiments, the first solvent may be a low vaporpressure solvent such as, for example, terpineol, diethylene glycol,ethylene glycol, hexylene glycol, N-methyl-2-pyrrolidone, andtri(ethylene glycol)dimethyl ether. A high vapor pressure solvent allowsrapid removal of the solvent by drying and/or evaporation attemperatures below the boiling point. High vapor pressure solvents mayinclude, for example, acetone, tetrahydrofuran, toluene, xylene,ethanol, methanol, 2-butanone and water.

In embodiments where mixed liquids comprising a first solvent, secondsolvent, third solvent, and so forth are used in the reaction mixture,promoting the change of the wet film and forming the dry SOF maycomprise, for example, heating the wet film to a temperature above theboiling point of the reaction mixture to form the dry SOF film; orheating the wet film to a temperature above the boiling point of thesecond solvent (below the temperature of the boiling point of the firstsolvent) in order to remove the second solvent while substantiallyleaving the first solvent and then after substantially removing thesecond solvent, removing the first solvent by heating the resultingcomposition at a temperature either above or below the boiling point ofthe first solvent to form the dry SOF film; or heating the wet filmbelow the boiling point of the second solvent in order to remove thesecond solvent (which is a high vapor pressure solvent) whilesubstantially leaving the first solvent and, after removing the secondsolvent, removing the first solvent by heating the resulting compositionat a temperature either above or below the boiling point of the firstsolvent to form the dry SOF film.

The term “substantially removing” refers to, for example, the removal ofat least 90% of the respective solvent, such as about 95% of therespective solvent. The term “substantially leaving” refers to, forexample, the removal of no more than 2% of the respective solvent, suchas removal of no more than 1% of the respective solvent.

These mixed liquids may be used to slow or speed up the rate ofconversion of the wet layer to the SOF in order to manipulate thecharacteristics of the SOFs. For example, in condensation andaddition/elimination linking chemistries, liquids such as water, 1°, 2°,or 3° alcohols (such as methanol, ethanol, propanol, isopropanol,butanol, 1-methoxy-2-propanol, tert-butanol) may be used.

Optionally a catalyst may be present in the reaction mixture to assistthe promotion of the wet layer to the dry SOF. Selection and use of theoptional catalyst depends on the functional groups on the molecularbuilding blocks. Catalysts may be homogeneous (dissolved) orheterogeneous (undissolved or partially dissolved) and include Bronstedacids (HCl (aq), acetic acid, p-toluenesulfonic acid, amine-protectedp-toluenesulfonic acid such as pyrridium p-toluenesulfonate,trifluoroacetic acid); Lewis acids (boron trifluoroetherate, aluminumtrichloride); Bronsted bases (metal hydroxides such as sodium hydroxide,lithium hydroxide, potassium hydroxide; 1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine);Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze); metalsalts (FeCl₃, AuCl₃); and metal complexes (ligated palladium complexes,ligated ruthenium catalysts). Typical catalyst loading ranges from about0.01% to about 25%, such as from about 0.1% to about 5% of the molecularbuilding block loading in the reaction mixture. The catalyst may or maynot be present in the final SOF composition.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF. Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. The terms “additive” or“secondary component,” refer, for example, to atoms or molecules thatare not covalently bound in the SOF, but are randomly distributed in thecomposition. In embodiments, secondary components such as conventionaladditives may be used to take advantage of the known propertiesassociated with such conventional additives. Such additives may be usedto alter the physical properties of the SOF such as electricalproperties (conductivity, semiconductivity, electron transport, holetransport), surface energy (hydrophobicity, hydrophilicity), tensilestrength, and thermal conductivity; such additives may include impactmodifiers, reinforcing fibers, lubricants, antistatic agents, couplingagents, wetting agents, antifogging agents, flame retardants,ultraviolet stabilizers, antioxidants, biocides, dyes, pigments,odorants, deodorants, nucleating agents and the like.

In embodiments, the SOF may contain antioxidants as a secondarycomponent to protect the SOF from oxidation. Examples of suitableantioxidants include (1) N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy hydrocinnamamide) (IRGANOX 1098,available from Ciba-Geigy Corporation), (2)2,2-bis(4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl)propane (TOPANOL-205, available from ICI America Corporation), (3)tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl) isocyanurate (CYANOX1790, 41,322-4, LTDP, Aldrich D12,840-6), (4) 2,2′-ethylidenebis(4,6-di-tert-butylphenyl) fluoro phosphonite (ETHANOX-398, availablefrom Ethyl Corporation), (5)tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyl diphosphonite (ALDRICH46,852-5; hardness value 90), (6) pentaerythritol tetrastearate (TCIAmerica #P0739), (7) tributylammonium hypophosphite (Aldrich 42,009-3),(8) 2,6-di-tert-butyl-4-methoxyphenol (Aldrich 25,106-2), (9)2,4-di-tert-butyl-6-(4-methoxybenzyl) phenol (Aldrich 23,008-1), (10)4-bromo-2,6-dimethylphenol (Aldrich 34,951-8), (11)4-bromo-3,5-didimethylphenol (Aldrich B6,420-2), (12)4-bromo-2-nitrophenol (Aldrich 30,987-7), (13) 4-(diethylaminomethyl)-2,5-dimethylphenol (Aldrich 14,668-4), (14)3-dimethylaminophenol (Aldrich D14,400-2), (15)2-amino-4-tert-amylphenol (Aldrich 41,258-9), (16)2,6-his(hydroxymethyl)-p-cresol (Aldrich 22,752-8), (17)2,2′-methylenediphenol (Aldrich B4,680-8), (18)5-(diethylamino)-2-nitrosophenol (Aldrich 26,951-4), (19)2,6-dichloro-4-fluorophenol (Aldrich 28,435-1), (20) 2,6-dibromo fluorophenol (Aldrich 26,003-7), (21) a trifluoro-o-cresol (Aldrich 21,979-7),(22) 2-bromo-4-fluorophenol (Aldrich 30,246-5), (23) 4-fluorophenol(Aldrich. F1,320-7), (24) 4-chlorophenyl-2-chloro-1,1,2-tri-fluoroethylsulfone (Aldrich 13,823-1), (25) 3,4-difluoro phenylacetic acid (Aldrich29,043-2), (26) 3-fluorophenylacetic acid (Aldrich 24,804-5), (27)3,5-difluoro phenylacetic acid (Aldrich 29,044-0), (28)2-fluorophenylacetic acid (Aldrich 20,894-9), (29)2,5-bis(trifluoromethyl)benzoic acid (Aldrich 32,527-9), (30)ethyl-2-(4-(4-(trifluoromethyl) phenoxy) phenoxy)propionate (Aldrich25,074-0), (31) tetrakis (2,4-di-tert-butyl phenyl)-4,4′-biphenyldiphosphonite (Aldrich 46,852-5), (32) 4-tert-amyl phenol (Aldrich15,384-2), (33) 3-(2H-benzotriazol-2-yl)-4-hydroxy phenethylalcohol(Aldrich 43,071-4), NAUGARD 76, NAUGARD 445, NAUGARD 512, and NAUGARD524 (manufactured by Uniroyal Chemical Company), and the like, as wellas mixtures thereof. The antioxidant, when present, may be present inthe SOF composite in any desired or effective amount, such as from about0.25 percent to about 10 percent by weight of the SOF or from about 1percent to about 5 percent by weight of the SOF.

In embodiments, the SOF may further comprise any suitable polymericmaterial known in the art as a secondary component, such aspolycarbonates, acrylate polymers, vinyl polymers, cellulose polymers,polyesters, polysiloxanes, polyamides, polyurethanes, polystyrenes,polystyrene, polyolefins, fluorinated hydrocarbons (fluorocarbons), andengineered resins as well as block, random or alternating copolymersthereof. The SOF composite may comprise homopolymers, higher orderpolymers, or mixtures thereof, and may comprise one species of polymericmaterial or mixtures of multiple species of polymeric material, such asmixtures of two, three, four, five or more multiple species of polymericmaterial. In embodiments, suitable examples of the about polymersinclude, for example, crystalline and amorphous polymers, or a mixturesthereof. In embodiments, the polymer is a fluoroelastomer.

Suitable fluoroelastomers are those described in detail in U.S. Pat.Nos. 5,166,031, 5,281,506, 5,366,772, 5,370,931, 4,257,699, 5,017,432and 5,061,965, the disclosures each of which are incorporated byreference herein in their entirety. The amount of fluoroelastomercompound present in the SOF, in weight percent total solids, is fromabout 1 to about 50 percent, or from about 2 to about 10 percent byweight of the SOF. Total solids, as used herein, includes the amount ofsecondary components and SOF.

In embodiments, examples of styrene-based monomer and acrylate-basedmonomers include, for example, poly(styrene-alkyl acrylate),poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate),poly(styrene-alkyl acrylate-acrylic acid),poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkylmethacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate),poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkylacrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkylacrylate-acrylonitrile-acrylic acid),poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkylacrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene),poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene),poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene),poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene),poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene),poly(butyl acrylate-butadiene), poly(styrene-isoprene),poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene),poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene),poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene),poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), andpoly(butyl acrylate-isoprene); poly(styrene-propyl acrylate),poly(styrene-butyl acrylate), polystyrene-butadiene-acrylic acid),poly(styrene-butadiene-methacrylic acid),polystyrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butylacrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid),poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butylacrylate-acrylonitrile-acrylic acid), and other similar polymers.

Further examples of the various polymers that are suitable for use as asecondary component in SOFs include polyethylene terephthalate,polybutadienes, polysulfones, polyarylethers, polyarylsulfones,polyethersulfones, polycarbonates, polyethylenes, polypropylenes,polydecene, polydodecene, polytetradecene, polyhexadecene, polyoctadene,and polycyclodecene, polyolefin copolymers, mixtures of polyolefins,functional polyolefins, acidic polyolefins, branched polyolefins,polymethylpentenes, polyphenylene sulfides, polyvinyl acetates,polyvinylbutyrals, polysiloxanes, polyacrylates, polyvinyl acetals,polyamides, polyimides, polystyrene and acrylonitrile copolymers,polyvinylchlorides, polyvinyl alcohols, poly-N-vinylpyrrolidinone)s,vinylchloride and vinyl acetate copolymers, acrylate copolymers,poly(amideimide), styrene-butadiene copolymers,vinylidenechloride-vinylchloride copolymers,vinylacetate-vinylidenechloride copolymers, polyvinylcarbazoles,polyethylene-terephthalate, polypropylene-terephthalate,polybutylene-terephthalate, polypentylene-terephthalate,polyhexalene-terephthalate, polyheptadene-terephthalate,polyoctalene-terephthalate, polyethylene-sebacate, polypropylenesebacate, polybutylene-sebacate, polyethylene-adipate,polypropylene-adipate, polybutylene-adipate, polypentylene-adipate,polyhexalene-adipate, polyheptadene-adipate, polyoctalene-adipate,polyethylene-glutarate, polypropylene-glutarate, polybutylene-glutarate,polypentylene-glutarate, polyhexalene-glutarate,polyheptadene-glutarate, polyoctalene-glutarate polyethylene-pimelate,polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate,polyhexalene-pimelate, polyheptadene-pimelate, poly(propoxylatedbisphenol-fumarate), poly(propoxylated bisphenol-succinate),poly(propoxylated bisphenol-adipate), poly(propoxylatedbisphenol-glutarate), SPAR™ (Dixie Chemicals), BECKOSOL™ (ReichholdChemical Inc), ARAKOTE™ (Ciba-Geigy Corporation), HETRON™ (AshlandChemical), PARAPLEX™ (Rohm & Hass), POLYLITE™ (Reichhold Chemical Inc),PLASTHALL™ (Rohm & Hass), CYGAL™ (American Cyanamide), ARMCO™ (ArmcoComposites), ARPOL™ (Ashland Chemical), CELANEX™ (Celanese Eng), RYNITE™(DuPont), STYPOL™ (Freeman Chemical Corporation) mixtures thereof andthe like.

In embodiments, the secondary components, including polymers may bedistributed homogeneously, or heterogeneously, such as in a linear ornonlinear gradient in the SOF. In embodiments, the polymers may beincorporated into the SOF in the form of a fiber, or a particle whosesize may range from about 50 nm to about 2 mm. The polymers, whenpresent, may be present in the SOF composite in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe SOF or from about 1 percent to about 15 percent by weight of theSOF.

In embodiments, the SOF may further comprise carbon nanotubes ornanofiber aggregates, which are microscopic particulate structures ofnanotubes, as described in U.S. Pat. Nos. 5,165,909; 5,456,897;5,707,916; 5,877,110; 5,110,693; 5,500,200 and 5,569,635, all of whichare hereby entirely incorporated by reference.

In embodiments, the SOF may further comprise metal particles as asecondary component; such metal particles include noble and non-noblemetals and their alloys. Examples of suitable noble metals include,aluminum, titanium, gold, silver, platinum, palladium and their alloys.Examples of suitable non-noble metals include, copper, nickel, cobalt,lead, iron, bismuth, zinc, ruthenium, rhodium, rubidium, indium, andtheir alloys. The size of the metal particles may range from about 1 nmto 1 mm and their surfaces may be modified by stabilizing molecules ordispersant molecules or the like. The metal particles, when present, maybe present in the SOF composite in any desired or effective amount, suchas from about 0.25 percent to about 70 percent by weight of the SOF orfrom about 1 percent to about 15 percent by weight of the SOF.

In embodiments, the SOF may further comprise oxides and sulfides assecondary components. Examples of suitable metal oxides include,titanium dioxide (titania, rutile and related polymorphs), aluminumoxide including alumina, hydradated alumina, and the like, silicon oxideincluding silica, quartz, cristobalite, and the like, aluminosilicatesincluding zeolites, talcs, and clays, nickel oxide, iron oxide, cobaltoxide. Other examples of oxides include glasses, such as silica glass,borosilicate glass, aluminosilicate glass and the like. Examples ofsuitable sulfides include nickel sulfide, lead sulfide, cadmium sulfide,tin sulfide, and cobalt sulfide. The diameter of the oxide and sulfidematerials may range from about 50 nm to 1 mm and their surfaces may bemodified by stabilizing molecules or dispersant molecules or the like.The oxides, when present, may be present in the SOF composite in anydesired or effective amount, such as from about 0.25 percent to about 20percent by weight of the SOF or from about 1 percent to about 15 percentby weight of the SOF.

In embodiments, the SOF may further comprise metalloid or metal-likeelements from the periodic table. Examples of suitable metalloidelements include, silicon, selenium, tellurium, tin, lead, germanium,gallium, arsenic, antimony and their alloys or intermetallics. The sizeof the metal particles may range from about 10 nm to 1 mm and theirsurfaces may be modified by stabilizing molecules or dispersantmolecules or the like. The metalloid particles, when present, may bepresent in the SOF composite in any desired or effective amount, such asfrom about 0.25 percent to about 10 percent by weight of the SOF or fromabout 1 percent to about 5 percent by weight of the SOF.

In embodiments, the SOF may further comprise hole transport molecules orelectron acceptors as a secondary component, such charge transportmolecules include for example a positive hole transporting materialselected from compounds having in the main chain or the side chain apolycyclic aromatic ring such as anthracene, pyrene, phenanthrene,coronene, and the like, or a nitrogen-containing hetero ring such asindole, carbazole, oxazole, isoxazole, thiazole, imidazole, pyrazole,oxadiazole, pyrazoline, thiadiazole, triazole, and hydrazone compounds.Typical hole transport materials include electron donor materials, suchas carbazole; N-ethyl carbazole; N-isopropyl carbazole; N-phenylcarbazole; tetraphenylpyrene; 1-methyl pyrene; perylene; chrysene;anthracene; tetraphene; 2-phenyl naphthalene; azopyrene; 1-ethyl pyrene;acetyl pyrene; 2,3-benzochrysene; 2,4-benzopyrene; 1,4-bromopyrene;poly(N-vinylcarbazole); poly(vinylpyrene); poly(vinyltetraphene);poly(vinyltetracene) and poly(vinylperylene). Suitable electrontransport materials include electron acceptors such as2,4,7-trinitro-9-fluorenone; 2,4,5,7-tetranitro-fluorenone;dinitroanthracene; dinitroacridene; tetracyanopyrene;dinitroanthraquinone; and butylcarbonylfluorenemalononitrile, see U.S.Pat. No. 4,921,769 the disclosure of which is incorporated herein byreference in its entirety. Other hole transporting materials includearylamines described in U.S. Pat. No. 4,265,990 the disclosure of whichis incorporated herein by reference in its entirety, such asN,N′-diphenyl-N,N′-bis(alkylphenyl)-(1,1′-biphenyl)-4,4′-diamine whereinalkyl is selected from the group consisting of methyl, ethyl, propyl,butyl, hexyl, and the like. Hole transport molecules of the typedescribed in, for example, U.S. Pat. Nos. 4,306,008; 4,304,829;4,233,384; 4,115,116; 4,299,897; 4,081,274, and 5,139,910, the entiredisclosures of each are incorporated herein by reference. Other knowncharge transport layer molecules may be selected, reference for exampleU.S. Pat. Nos. 4,921,773 and 4,464,450 the disclosures of which areincorporated herein by reference in their entireties. The hole transportmolecules or electron acceptors, when present, may be present in the SOFcomposite in any desired or effective amount, such as from about 0.25percent to about 50 percent by weight of the SOF or from about 1 percentto about 20 percent by weight of the SOF.

In embodiments, the SOF may further comprise biocides as a secondarycomponent. Biocides may be present in amounts of from about 0.1 to about1.0 percent by weight of the SOF. Suitable biocides include, forexample, sorbic acid, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanechloride, commercially available as DOWICIL 200 (Dow Chemical Company),vinylene-bis thiocyanate, commercially available as CYTOX 3711 (AmericanCyanamid Company), disodium ethylenebis-dithiocarbamate, commerciallyavailable as DITHONE D14 (Rohm & Haas Company),bis(trichloromethyl)sulfone, commercially available as BIOCIDE N-1386(Stauffer Chemical Company), zinc pyridinethione, commercially availableas zinc omadine (Olin Corporation), 2-bromo-t-nitropropane-1,3-diol,commercially available as ONYXIDE 500 (Onyx Chemical Company), BOSQUATMB50 (Louza, Inc.), and the like.

In embodiments, the SOF may further comprise small organic molecules asa secondary component; such small organic molecules include thosediscussed above with respect to the first and second solvents. The smallorganic molecules, when present, may be present in the SOF in anydesired or effective amount, such as from about 0.25 percent to about 50percent by weight of the SOF or from about 1 percent to about 10 percentby weight of the SOF.

When present, the secondary components or additives may each, or incombination, be present in the composition in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe composition or from about 1 percent to about 20 percent by weight ofthe composition.

SOFs may be modified with secondary components (dopants and additives,such as, hole transport molecules (mTBD), polymers (polystyrene),nanoparticles (C60 Buckminster fullerene), small organic molecules(biphenyl), metal particles (copper micropowder), and electron acceptors(quinone)) to give composite structured organic films. Secondarycomponents may be introduced to the liquid formulation that is used togenerate a wet film in which a change is promoted to form the SOF.Secondary components (dopants, additives, etc.) may either be dissolvedor undissolved (suspended) in the reaction mixture. Secondary componentsare not bonded into the network of the film. For example, a secondarycomponent may be added to a reaction mixture that contains a pluralityof building blocks having four methoxy groups (—OMe) on a segment, suchas N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine, which uponpromotion of a change in the wet film, exclusively react with the twoalcohol (—OH) groups on a building block, such as 1,4-benzenedimethanol,which contains a p-xylyl segment. The chemistry that is occurring tolink building blocks is an acid catalyzed transetherfication reaction.Because —OH groups will only react with —OMe groups (and vice versa) andnot with the secondary component, these molecular building blocks canonly follow one pathway. Therefore, the SOF is programmed to ordermolecules in a way that leaves the secondary component incorporatedwithin and/or around the SOF structure. This ability to patternmolecules and incorporate secondary components affords superiorperformance and unprecedented control over properties compared toconventional polymers and available alternatives.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF. Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. In contrast to capping units, theterms “additive” or “secondary component,” refer, for example, to atomsor molecules that are not covalently bound in the SOF, but are randomlydistributed in the composition. Suitable secondary components andadditives are described in U.S. patent application Ser. No. 12/716,324,entitled “Composite Structured Organic Films,” the disclosure of whichis totally incorporated herein by reference in its entirety.

In embodiments, the secondary components may have similar or disparateproperties to accentuate or hybridize (synergistic effects orameliorative effects as well as the ability to attenuate inherent orinclined properties of the capped SOF) the intended property of thecapped SOF to enable it to meet performance targets. For example, dopingthe capped SOFs with antioxidant compounds will extend the life of thecapped SOF by preventing chemical degradation pathways. Additionally,additives maybe added to improve the morphological properties of thecapped SOF by tuning the reaction occurring during the promotion of thechange of the reaction mixture to form the capped SOF.

Process Action B: Depositing the Reaction Mixture as a Wet Film

The reaction mixture may be applied as a wet film to a variety ofsubstrates, such as print head front faces, using a number of liquiddeposition techniques. Alternatively, the porous SOF may be prepared andthen attached to the print head front face. The thickness of the SOF isdependant on the thickness of the wet film and the molecular buildingblock loading in the reaction mixture. The thickness of the wet film isdependent on the viscosity of the reaction mixture and the method usedto deposit the reaction mixture as a wet film.

Substrates include, for example, polymers, papers, metals and metalalloys, doped and undoped forms of elements from Groups III-VI of theperiodic table, metal oxides, metal chalcogenides, and previouslyprepared SOFs or capped SOFs. Examples of polymer film substratesinclude polyesters, polyolefins, polycarbonates, polystyrenes,polyvinylchloride, block and random copolymers thereof, and the like.Examples of metallic surfaces include metallized polymers, metal foils,metal plates; mixed material substrates such as metals patterned ordeposited on polymer, semiconductor, metal oxide, or glass substrates.Examples of substrates comprised of doped and undoped elements fromGroups IH-VI of the periodic table include, aluminum, silicon, siliconn-doped with phosphorous, silicon p-doped with boron, tin, galliumarsenide, lead, gallium indium phosphide, and indium. Examples of metaloxides include silicon dioxide, titanium dioxide, indium tin oxide, tindioxide, selenium dioxide, and alumina. Examples of metal chalcogenidesinclude cadmium sulfide, cadmium telluride, and zinc selenide.Additionally, it is appreciated that chemically treated or mechanicallymodified forms of the above substrates remain within the scope ofsurfaces that may be coated with the reaction mixture.

In embodiments, the substrate may be composed of, for example, silicon,glass plate, plastic film or sheet. For structurally flexible devices, aplastic substrate such as polyester, polycarbonate, polyimide sheets andthe like may be used. The thickness of the substrate may be from around10 micrometers to over 10 millimeters with an exemplary thickness beingfrom about 50 to about 100 micrometers, especially for a flexibleplastic substrate, and from about 1 to about 10 millimeters for a rigidsubstrate such as glass or silicon.

The reaction mixture may be applied to the substrate using a number ofliquid deposition techniques including, for example, spin coating, bladecoating, web coating, dip coating, cup coating, rod coating, screenprinting, ink jet printing, spray coating, stamping and the like. Themethod used to deposit the wet layer depends on the nature, size, andshape of the substrate and the desired wet layer thickness. Thethickness of the wet layer can range from about 10 nm to about 5 mm,such as from about 100 nm to about 1 mm, or from about 1 μm to about 500μm.

In embodiments, the capping unit and/or secondary component may beintroduced following completion of the above described process action B.The incorporation of the capping unit and/or secondary component in thisway may be accomplished by any means that serves to distribute thecapping unit and/or secondary component homogeneously, heterogeneously,or as a specific pattern over the wet film. Following introduction ofthe capping unit and/or secondary component subsequent process actionsmay be carried out resuming with process action C.

For example, following completion of process action B (i.e., after thereaction mixture may be applied to the substrate), capping unit(s)and/or secondary components (dopants, additives, etc.) may be added tothe wet layer by any suitable method, such as by distributing (e.g.,dusting, spraying, pouring, sprinkling, etc., depending on whether thecapping unit and/or secondary component is a particle, powder or liquid)the capping unit(s) and/or secondary component on the top the wet layer.The capping units and/or secondary components may be applied to theformed wet layer in a homogeneous or heterogeneous manner, includingvarious patterns, wherein the concentration or density of the cappingunits) and/or secondary component is reduced in specific areas, such asto form a pattern of alternating bands of high and low concentrations ofthe capping unit(s) and/or secondary component of a given width on thewet layer. In embodiments, the application of the capping unit(s) and/orsecondary component to the top of the wet layer may result in a portionof the capping unit(s) and/or secondary component diffusing or sinkinginto the wet layer and thereby forming a heterogeneous distribution ofcapping unit(s) and/or secondary component within the thickness of theSOF, such that a linear or nonlinear concentration gradient may beobtained in the resulting SOF obtained after promotion of the change ofthe wet layer to a dry SOF. In embodiments, a capping unit(s) and/orsecondary component may be added to the top surface of a deposited wetlayer, which upon promotion of a change in the wet film, results in anSOF having an heterogeneous distribution of the capping unit(s) and/orsecondary component in the dry SOF. Depending on the density of the wetfilm and the density of the capping unit(s) and/or secondary component,a majority of the capping unit(s) and/or secondary component may end upin the upper half (which is opposite the substrate) of the dry SOF or amajority of the capping unit(s) and/or secondary component may end up inthe lower half (which is adjacent to the substrate) of the dry SOF.

Process Action C: Promoting the Change of Wet Film to the Dry SOF

The term “promoting” refers, for example, to any suitable technique tofacilitate a reaction of the molecular building blocks and/or pre-SOFs,such as a chemical reaction of the functional groups of the buildingblocks and/or pre-SOFs. In the case where a liquid needs to be removedto form the dry film, “promoting” also refers to removal of the liquid.Reaction of the molecular building blocks and/or pre-SOFs and removal ofthe liquid can occur sequentially or concurrently. In certainembodiments, the liquid is also one of the molecular building blocks andis incorporated into the SOF. The term “dry SOF” refers, for example, tosubstantially dry SOFs, for example, to a liquid content less than about5% by weight of the SOF, or to a liquid content less than 2% by weightof the SOF.

In embodiments, the dry SOF or a given region of the dry SOF (such asthe surface to a depth equal to of about 10% of the thickness of the SOFor a depth equal to of about 5% of the thickness of the SOF, the upperquarter of the SOF, or the regions discussed above) has a molar ratio ofcapping units to segments of from about 1:100 to about 1:1, such as fromabout 1:50 to about 1:2, or from about 1:20 to 1:4.

Promoting the wet layer to form a dry SOF may be accomplished by anysuitable technique. Promoting the wet layer to form a dry SOF typicallyinvolves thermal treatment including, for example, oven drying, infraredradiation (IR), and the like with temperatures ranging from 40 to 350°C. and from 60 to 200° C. and from 85 to 160° C. The total heating timecan range from about four seconds to about 24 hours, such as from oneminute to 120 minutes, or from three minutes to 60 minutes.

In embodiments where a secondary component is present, the molecularsize of the secondary component may be selected such that during thepromotion of the wet layer to form a dry SOF the secondary component istrapped within the framework of the SOF such that the trapped secondarycomponent will not leach from the SOF during exposure to a liquid toneror solvent.

IR promotion of the wet layer to the COF film may be achieved using anIR heater module mounted over a belt transport system. Various types ofIR emitters may be used, such as carbon IR emitters or short wave IRemitters (available from Heraerus). Additional exemplary informationregarding carbon IR emitters or short wave IR emitters is summarized inthe following Table (Table 1).

TABLE 1 Information regarding carbon IR emitters or short wave IRemitters Number of Module Power IR lamp Peak Wavelength lamps (kW)Carbon 2.0 micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron 3 - twintube 4.5

Process Action D: Optionally Removing the SOF from the Coating Substrateto Obtain a Free-Standing SOF

In embodiments, a free-standing SOF is desired. Free-standing SOFs maybe obtained when an appropriate low adhesion substrate is used tosupport the deposition of the wet layer. Appropriate substrates thathave low adhesion to the SOF may include, for example, metal foils,metalized polymer substrates, release papers and SOFs, such as SOFsprepared with a surface that has been altered to have a low adhesion ora decreased propensity for adhesion or attachment. Removal of the SOFfrom the supporting substrate may be achieved in a number of ways bysomeone skilled in the art. For example, removal of the SOF from thesubstrate may occur by starting from a corner or edge of the film andoptionally assisted by passing the substrate and SOF over a curvedsurface.

Process Action E: Optionally Processing the Free-Standing SOF into aRoll

Optionally, a free-standing SOF or a SOF supported by a flexiblesubstrate may be processed into a roll. The SOF may be processed into aroll for storage, handling, and a variety of other purposes. Thestarting curvature of the roll is selected such that the SOF is notdistorted or cracked during the rolling process.

Process Action F: Optionally Cutting and Seaming the SOF into a Shape,such as a Belt

The method for cutting and seaming the SOF is similar to that describedin U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995 (for polymer films),the disclosure of which is herein totally incorporated by reference. AnSOF belt may be fabricated from a single SOF, a multi layer SOF or anSOF sheet cut from a web. Such sheets may be rectangular in shape or anyparticular shape as desired. All sides of the SOF(s) may be of the samelength, or one pair of parallel sides may be longer than the other pairof parallel sides. The SOF(s) may be fabricated into shapes, such as abelt by overlap joining the opposite marginal end regions of the SOFsheet. A seam is typically produced in the overlapping marginal endregions at the point of joining. Joining may be affected by any suitablemeans. Typical joining techniques include, for example, welding(including ultrasonic), gluing, taping, pressure heat fusing and thelike. Methods, such as ultrasonic welding, are desirable general methodsof joining flexible sheets because of their speed, cleanliness (nosolvents) and production of a thin and narrow seam.

Process Action G: Optionally Using a SOF as a Substrate for SubsequentSOF Formation Processes

A SOF may be used as a substrate in the SOF forming process to afford amulti-layered structured organic film. The layers of a multi-layered SOFmay be chemically bound in or in physical contact. Chemically bound,multi-layered SOFs are formed when functional groups present on thesubstrate SOF surface can react with the molecular building blockspresent in the deposited wet layer used to form the second structuredorganic film layer. Multi-layered SOFs in physical contact may notchemically bound to one another.

A SOF substrate may optionally be chemically treated prior to thedeposition of the wet layer to enable or promote chemical attachment ofa second SOF layer to form a multi-layered structured organic film.

Alternatively, a SOF substrate may optionally be chemically treatedprior to the deposition of the wet layer to disable chemical attachmentof a second SOF layer (surface pacification) to form a physical contactmulti-layered SOF.

Other methods, such as lamination of two or more SOFs, may also be usedto prepare physically contacted multi-layered SOFs.

Process Action H: Optionally Activating the Dry SOF

In embodiments, the dry SOF may optionally be activated in order emptythe plurality of pores and remove any residual chemical species that mayremain after formation of the SOF. In embodiments, activating the drySOF may comprise soaking the SOF in a solvent, such as an organicsolvent (e.g., a volatile organic solvent), for a predetermined amountof time, such as for about 12 hours or more, or for about 24 hours ormore. Optionally, the solvent may be refreshed and the soaking step maybe repeated until the elution concentration of any residual species inthe solvent that the SOF is immersed in is at a level of less than 10ppm, such as less than 1 ppm, or less than 0.1 ppm. In embodiments, theSOF may be optionally heated (with or without reduced pressure) at oneor more temperatures either before or after any of the above soakingsteps. In embodiments, the heating temperature may be selected based onthe thermal properties of the dry SOF and the identity of the soakingsolvent. For example, generally dry SOFs may be heated to a temperature150° C. for 12 hr, and then heated at 60° C. for 12 hours at 10⁻⁵ torr,without any degradation.

Patterned SOF Composition

An embodiment of the disclosure is to attain a SOF wherein themicroscopic arrangement of segments is patterned. The term “patterning”refers, for example, to the sequence in which segments are linkedtogether. A patterned SOF would therefore embody a composition wherein,for example, segment A is only connected to segment B, and conversely,segment B is only connected to segment A. Further, a system wherein onlyone segment exists, say segment A, is employed is will be patternedbecause A is intended to only react with A. In principle a patterned SOFmay be achieved using any number of segment types. The patterning ofsegments may be controlled by using molecular building blocks whosefunctional group reactivity is intended to compliment a partnermolecular building block and wherein the likelihood of a molecularbuilding block to react with itself is minimized. The aforementionedstrategy to segment patterning is non-limiting. Instances where aspecific strategy to control patterning has not been deliberatelyimplemented are also embodied herein.

A patterned film may be detected using spectroscopic techniques that arecapable of assessing the successful formation of linking groups in aSOF. Such spectroscopies include, for example, Fourier-transfer infraredspectroscopy, Raman spectroscopy, and solid-state nuclear magneticresonance spectroscopy. Upon acquiring a data by a spectroscopictechnique from a sample, the absence of signals from functional groupson building blocks and the emergence of signals from linking groupsindicate the reaction between building blocks and the concomitantpatterning and formation of an SOF.

Different degrees of patterning are also embodied. Full patterning of aSOF will be detected by the complete absence of spectroscopic signalsfrom building block functional groups. Also embodied are SOFs havinglowered degrees of patterning wherein domains of patterning exist withinthe SOF. SOFs with domains of patterning, when measuredspectroscopically, will produce signals from building block functionalgroups which remain unmodified at the periphery of a patterned domain.

It is appreciated that a very low degree of patterning is associatedwith inefficient reaction between building blocks and the inability tofaun a film. Therefore, successful implementation of the process of thepresent disclosure requires appreciable patterning between buildingblocks within the SOF. The degree of necessary patterning to form a SOFis variable and can depend on the chosen building blocks and desiredlinking groups. The minimum degree of patterning required is thatrequired to form a film using the process described herein, and may bequantified as formation of about 20% or more of the intended linkinggroups, such as about 40% or more of the intended linking groups orabout 50% or more of the intended linking groups; the nominal degree ofpatterning embodied by the present disclosure is formation of about 60%of the intended linking group, such as formation of about 100% of theintended linking groups. Formation of linking groups may be detectedspectroscopically as described earlier in the embodiments.

Production of a Porous SOF

EXAMPLE 1

(Action A) Preparation of the liquid containing reaction mixture. Thefollowing were combined: the building block(4,4′,4″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl))tetramethanol[segment=(4,4′,4″,4′″-(biphenyl-4,4′-diylbis(azanetriyl))tetrakis(benzene-4,1-diyl);Fg=alcohol (—OH); (1.48 g, 2.4 mmol)], and 8.3 g of N-methylpyridinone.The mixture was shaken and heated to 40° C. until a homogenous solutionresulted. Upon cooling to room temperature, the solution was filteredthrough a 0.45 micron PTFE membrane. To the filtered solution was addedan acid catalyst delivered as 0.15 g of a 10 wt % solution ofp-toluenesulfonic acid in N-methylpyridinone to yield the liquidcontaining reaction mixture.

(Action B) Deposition of reaction mixture as a wet film. The reactionmixture was applied to the reflective side of a metalized (Tizr) MYLAR™substrate using a constant velocity draw down coater outfitted with abird bar having a 10 mil gap.

(Action C) Promotion of the change of the wet film to a thy SOF. Thesubstrate supporting the wet layer was rapidly transferred to anactively vented oven preheated to 140° C. and left to heat for 40minutes. These actions provided a dry SOF having a thickness rangingfrom about 5-10 microns. The color of the SOF was green-yellow.

The dry SOF was activated in order empty the pores with any chemicalentities that may reside therein following SOF formation. The dry SOFwas soaked in acetone for 12 hours, and then acetone was refreshed and asecond soaking for 24 h was performed. Following acetone soaking the drySOF was heated in a 150° C. for 12 hr, and then heated at 60° C. for 12hours at 10⁻⁵ torr.

The permanent porosity of these films was measured using a state-of-theart gas adsorption method wherein the activated sample is dosed withcarbon dioxide under supercritical conditions to obtain a gas adsorptionisotherm (FIG. 2). Subsequent assessment of this isotherm using densityfunctional theory extracts metrical parameters of the material'sporosity.

The Langmuir surface area of the SOF was determined to be 155 m²/g(+/−1.7 m²/g). The reversibility of the isotherm (i.e. desorption ofcarbon dioxide gas) indicates that the pores are permanent and do notcollapse as is frequently the case in polymeric membranes.

Additionally from the isotherm in FIG. 2, the distribution of pore sizeswith in the SOF can be determined (FIG. 3). The pore size distributionin FIG. 3 indicates that two sizes of pores exist within in the SOF:about 6 angstroms (0.6 nm) and about 8.5 angstroms (0.85 nm). These poresizes are appropriate to host gas molecules like hydrogen and methanefor vehicular applications and are ideal for separating carbon dioxidefrom combustion waste gas streams using pressure swing adsorptionprocesses. The porosity of SOFs can be putatively adjusted by usingbuilding blocks that alter the internal pore structure within the SOF.For example, an SOF may be created with a more ‘open’ pore structurewithin the SOF by using other larger and/or divergent building blocksand linkers. Exemplary of molecular building block segments that supportincreased porosity include are depicted below:

It will be appreciated that several of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Variouspresently unforeseen or unanticipated alternatives, modifications,variations or improvements therein may be subsequently made by thoseskilled in the art which are also intended to be encompassed by thefollowing claims. Unless specifically recited in a claim, steps orcomponents of claims should not be implied or imported from thespecification or any other claims as to any particular order, number,position, size, shape, angle, color, or material.

1. A method for storing a gaseous entity, the method comprising:contacting the gaseous entity with a sorbent material, the sorbentmaterial comprising a porous structured organic film (SOF) comprising aplurality of segments including at least a first segment type and aplurality of linkers including at least a first linker type arranged asa covalent organic framework (COT), and a plurality of pores, whereinthe first segment type and/or the first linker type comprises at leastone atom that is not carbon, and the plurality of pores comprises aplurality of accessible sites for uptake and storage of the gaseousentity; and storing the gaseous entity for a predetermined duration. 2.The method of claim 1, wherein contacting the gaseous entity with asorbent material further comprises concentrating the gaseous entitybeyond the concentration observed for its natural compressibility. 3.The method of claim 2, wherein the gaseous chemical entity is present inthe SOF at a concentration from about 1.1 times greater than the naturalcompressibility of the gaseous chemical entity to about theconcentration of the gaseous chemical entity upon its liquification. 4.The method of claim 1, wherein predetermined duration is from aboutthirty seconds to about one year.
 5. The method of claim 1, wherein theuptake and storage of the chemical entity are reversible.
 6. The methodof claim 1, wherein the SOF comprises a thermal stability range of atleast up to 200° C. and/or a Langmuir surface area of from about 75 m²/gto about 3500 m²/g.
 7. The method of claim 1, wherein the porous SOF isprepared by: (a) preparing a liquid-containing reaction mixturecomprising: a plurality of molecular building blocks each comprising asegment and functional groups; (b) depositing the reaction mixture as awet film; (c) promoting change of the wet film to form a dry SOF; and(d) activating the dry SOF by emptying the plurality pores andsubstantially removing any residual chemical species that remain afterformation of the SOF.
 8. The method of claim 1, wherein the porous SOFis functionalized.
 9. The method of claim 1, the plurality of pores hasa unimodal or multi-modal size distribution.
 10. The method of claim 1,wherein the porous SOF is a capped SOF.
 11. The method of claim 1,wherein the plurality of linkers are selected from the group consistingof single atom linkers, single covalent bond linkers, double covalentbond linkers, ester linkers, ketone linkers, amide linkers, aminelinkers, imine linkers, ether linkers, urethane linkers, and carbonateslinkers; and the plurality of segments have a core selected from thegroup consisting of carbon, nitrogen, silicon, or phosphorous atomiccores, alkyl cores, fluoroalkyl cores, alkoxy cores, aryl cores,carbonate cores, carbocyclic cores, carbobicyclic cores, carbotricycliccores, and oligothiophene cores.
 12. The method of claim 1, wherein theSOF is a multi-layer sheet.
 13. The method of claim 12, wherein themulti-layer sheet is adapted to function as a storage material in atank. 14-20. (canceled)
 21. The method of claim 1, wherein the SOF is asingle-layer sheet.
 22. The method of claim 21, wherein the single-layersheet is adapted to function as a storage material in a tank.
 23. Amethod for storing a gaseous entity, the method comprising: contactingthe gaseous entity with a sorbent material, the sorbent materialcomprising a porous structured organic film (SOF) comprising a pluralityof segments including at least a first segment type and a plurality oflinkers including at least a first linker type arranged as a covalentorganic framework (COF), and a plurality of pores, wherein the gaseouschemical entity is present in the SOF at a concentration from about 1.1times greater than the natural compressibility of the gaseous chemicalentity to about the concentration of the gaseous chemical entity uponits liquification, the first segment type and/or the first linker typecomprises at least one atom that is not carbon, and the plurality ofpores comprises a plurality of accessible sites for uptake and storageof the gaseous entity; and storing the gaseous entity for apredetermined duration.
 24. The method of claim 23, whereinpredetermined duration is from about thirty seconds to about one year.25. The method of claim 23, wherein the uptake and storage of thechemical entity are reversible.
 26. The method of claim 23, wherein theSOF comprises a thermal stability range of at least up to 200° C. and/ora Langmuir surface area of from about 75 m²/g to about 3500 m²/g.